Triketone derivatives and herbicides

ABSTRACT

The present invention relates to a novel triketone derivative having a specific structure and a herbicide containing the triketone derivative as an active ingredient. The herbicide is effective for controlling weeds which inhibit growth of crop plants, inter alia, for paddy weeds such as  Sanwa millet  and  Scirups juncoides.

FIELD OF THE INVENTION

[0001] The present invention relates to a novel triketone derivative anda herbicide containing the triketone derivative as an active ingredient.More particularly, the invention relates to a triketone derivativeuseful for a herbicide effective on weeds which inhibit growth of cropplants, inter alia, for paddy field weeds such as Echinochloa crus-galliand Scirups juncoides, and to a herbicide containing the triketonederivative as an active ingredient.

BACKGROUND ART

[0002] Herbicides are important chemicals for facilitating weed controland enhancing productivity of field and garden crops. Therefore,development of herbicides which is safe and has excellentweed-controlling property even at a low dose have been actively carriedout for many years.

[0003] There is proposed a herbicide containing a triketone derivativehaving a bicyclic benzoyl structure as an active ingredient, for theherbicide has excellent safety to field crops and excellentweed-controlling activity to field weeds. For example, there is proposeda herbicide containing a compound disclosed in Japanese Patent No.2579663 and International Patent Publication WO97/08164 as an activeingredient, which herbicide has an excellent weed-controlling propertysuitable for growth of field crops. However, a herbicide containing sucha compound as an active ingredient has poor activity for controllingpaddy field weeds, and disadvantageously has insufficient safety to apaddy rice plant.

DISCLOSURE OF THE INVENTION

[0004] In view of the foregoing, an object of the present invention isto provide a herbicide containing a triketone derivative as an activeingredient, which herbicide can control a wide range of weeds at a lowdose and imparts a low level of chemical injury to cultivated crops,particularly a paddy rice plant.

[0005] In order to attain the above object, the present inventors haveconducted earnest studies, and have found that a triketone derivativehaving a specific chemical structure can control a wide range of weedsat a low dose and imparts a low level of chemical injury to cultivatedcrops. The present invention has accomplished based on this finding.

[0006] The present invention includes first and second aspects asdescribed below.

[0007] The first aspect of the present invention encompasses thefollowing.

[0008] (1) A triketone derivative represented by formula [I-1]:

[0009] wherein R represents a methyl group; each of X and Y represents ahydrogen atom, a halogen atom, a nitro group, an amino group, a cyanogroup, a hydroxy group, a mercapto group, —R¹, —OR¹, —SR¹, —SO₂R¹,—NR²R³, or —NHCOR¹, wherein R¹ represents a C1-C6 alkyl group which mayhave a branched structure, a cyclic structure, or an unsaturated bond, aC1-C6 haloalkyl group which may have a branched structure, a cyclicstructure, or an unsaturated bond, a phenyl group which may besubstituted, or a benzyl group which may be substituted; each of R² andR³ represents a hydrogen atom, a C1-C6 alkyl group which may have abranched structure, a cyclic structure, or an unsaturated bond, a C1-C6haloalkyl group which may have a branched structure, a cyclic structure,or an unsaturated bond, a phenyl group which may be substituted, or abenzyl group which may be substituted, or R² and R³ may be bonded toeach other to form a group having a cyclic structure; M represents ahydrogen atom, an alkali metal, an alkaline earth metal, or an organicbase; R⁴ represents a hydrogen atom or a C1-C6 alkyl group; and m is aninteger between 0 and 4 inclusive; provided that not all of X, Y, and R⁴simultaneously represent methyl groups.

[0010] (2) A triketone derivative represented by formula [I-2]:

[0011] wherein R, X, Y, M, and m have the same definitions as describedin relation to formula [I-1].

[0012] (3) A triketone derivative represented by formula [I-3]:

[0013] wherein R, X, M, R⁴, and m have the same definitions as describedin relation to formula [I-1].

[0014] (4) A triketone derivative represented by formula [I-4]:

[0015] wherein R represents a methyl group; each of X and Y represents ahydrogen atom, a halogen atom, a nitro group, a cyano group, —R¹, —OR¹,—SR¹, or —NR²R³, wherein R¹ represents a C1-C6 alkyl group which mayhave a branched structure, a cyclic structure, or an unsaturated bond, aC1-C6 haloalkyl group which may have a branched structure, a cyclicstructure, or an unsaturated bond, a phenyl group which may besubstituted, or a benzyl group which may be substituted; each of R² andR³ represents a hydrogen atom, a C1-C6 alkyl group which may have abranched structure, a cyclic structure, or an unsaturated bond, a C1-C6haloalkyl group which may have a branched structure, a cyclic structure,or an unsaturated bond, a phenyl group which may be substituted, or abenzyl group which may be substituted, or R² and R³ may be bonded toeach other to form a group having a cyclic structure; Z represents —OR¹,—SO_(p)R¹, —A(CH₂)_(n)QR¹, —NR²R³, —N(OR¹)R², —O(C═O)R¹, —O(C═O)OR¹,—O(C═O)SR¹, —O(C═O)NR²R³, or —O(C═S)NR²R³ (wherein R¹, R², and R³ havethe same definitions as described in relation to X and Y. each of A andQ represents an oxygen atom or a sulfur atom, p is 0, 1, or 2, n is 1 or2), —OM (wherein M represents a hydrogen atom, an alkali metal, analkaline earth metal, or an organic base), or a halogen atom; and m isan integer between 0 and 4 inclusive.

[0016] (5) A triketone derivative according to (4), wherein Z representsan —OM group (wherein M represents a hydrogen atom, an alkali metal, analkaline earth metal, or an organic base).

[0017] (6) A triketone derivative according to any one of (1), (2), (4),and (5), wherein Y represents a hydrogen atom, a C1-C6 alkyl group, or ahalogen atom.

[0018] (7) A triketone derivative according to any one of (1), (2), (4),and (5), wherein Y represents a hydrogen atom or a methyl group.

[0019] (8) A triketone derivative according to any one of (2), (4), and(5), wherein Y represents a hydrogen atom.

[0020] (9) A triketone derivative according to any one of (1) to (8),wherein X represents —R¹, —OR¹, or —SR¹.

[0021] (10) A triketone derivative according to (1) or (9), wherein Xrepresents a halogen atom or a methyl group.

[0022] (11) A triketone derivative according to any one of (1) to (10),wherein M represents a hydrogen atom.

[0023] (12) A herbicide containing a triketone derivative as recited inany one of (1) to (11) as an active ingredient.

[0024] (13) A herbicide for use in cultivation of a paddy rice plant,which herbicide contains a triketone derivative as recited in any one of(1) to (11) as an active ingredient.

[0025] The second aspect of the present invention encompasses thefollowing.

[0026] (1) A triketone derivative represented by formula [II-1]:

[0027] wherein R represents a methyl group; X represents a hydrogenatom, a halogen atom, a nitro group, an amino group, a cyano group, ahydroxy group, a mercapto group, —R¹, —OR¹, —SR¹, SO₂R¹, —NR²R³, or—NHCOR¹ (wherein R¹ represents a C1-C6 alkyl group which may have abranched structure, a cyclic structure, or an unsaturated bond, a C1-C6haloalkyl group which may have a branched structure, a cyclic structure,or an unsaturated bond, a phenyl group which may be substituted, or abenzyl group which may be substituted; each of R² and R³ represents ahydrogen atom, a C1-C6 alkyl group which may have a branched structure,a cyclic structure, or an unsaturated bond, a C1-C6 haloalkyl groupwhich may have a branched structure, a cyclic structure, or anunsaturated bond, a phenyl group which may be substituted, or a benzylgroup which may be substituted, or R² and R³ may be bonded to each otherto form a group having a cyclic structure);

[0028] G contains 3 to 5 ring-constituting atoms which form a 5- to7-membered saturated or unsaturated condensed ring including two carbonatoms of the benzene ring adjacent to G, wherein two or lessring-constituting atoms are selected from among nitrogen, oxygen, andsulfur, and the ring-constituting atoms may have one or moresubstituents selected from among a C1-C6 alkyl group, a C1-C6 haloalkylgroup, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a hydroxy group,a mercapto group, an oxo group, a thioxo group, a hydroxyimino group, aC1-C6 alkoxyimino group, a hydrazono group, a C1-C6 monoalkylhydrazonogroup, and a C1-C6 dialkylhydrazono group, and a carbon atom or theadjacent carbon atom of the ring-constituting atom may have asubstituent selected from among an ethylenedioxy group, anethylenedithio group, a propylenedioxy group, and a propylenedithiogroup, with these substituents optionally being substituted with ahalogen atom or a C1-C6 alkyl group;

[0029] Z¹ represents a halogen atom, —OR¹, —SO_(p)R¹, —A(CH₂)_(n)QR¹,—NR²R³, —N(OR¹)R², —O(C═O)R¹, —O(C═O)OR¹, —O(C═O)SR¹, —O(C═O)NR²R³, or—O(C═S)NR²R³ (wherein R¹, R², and R³ have the same definitions asdescribed in relation to X, each of A and Q represents an oxygen atom ora sulfur atom, p is 0, 1, or 2, n is 1 to 3), or a halogen atom; m is aninteger between 0 and 4 inclusive; and q is 1 or 2.

[0030] (2) A triketone derivative according to (1), which is representedby formula [II-2] or [II-3]:

[0031] wherein R, X, G, Z¹, m, and q have the same definitions asdescribed in relation to formula [II-1].

[0032] (3) A triketone derivative according to (1) or (2), which isrepresented by any one of formulas [II-4] to [II-9]:

[0033] wherein R, X, G, Z¹, m, and q have the same definitions asdescribed in relation to formula [II-1], each of G¹ to G⁴ represents anoptionally substituted atom that constitutes G in formula [II-1], and iis 0, 1, or 2.

[0034] (4) A triketone derivative according to any one of (1) to (3),wherein X represents a halogen atom, —R¹, —OR¹, or —SR¹.

[0035] (5) A triketone derivative according to (3) or (4), wherein eachof G¹ to G⁴ represents a ring-constituting atom having one or moresubstituents selected from the substituent group consisting of anunsubstituted or C1-C6 alkyl group, a C1-C6 alkoxy group, an oxo group,and a C1-C6 alkoxyimino group.

[0036] (6) A triketone derivative according to any one of (1) to (5),wherein Z¹ is selected from among a halogen atom, —OR¹, —SO_(p)R¹,—A(CH₂)_(n)QR¹, and —N(OR¹)R².

[0037] (7) A triketone derivative represented by formula [II-10]:

[0038] wherein R represents a methyl group; each of X and Y represents ahydrogen atom, a halogen atom, a nitro group, a cyano group, —R¹, —OR¹,—SR¹, or —NR²R³ (wherein R¹ represents a C1-C6 alkyl group which mayhave a branched structure, a cyclic structure, or an unsaturated bond, aC1-C6 haloalkyl group which may have a branched structure, a cyclicstructure, or an unsaturated bond, a phenyl group which may besubstituted, or a benzyl group which may be substituted, each of R² andR³ represents a hydrogen atom, a C1-C6 alkyl group which may have abranched structure, a cyclic structure, or an unsaturated bond, a C1-C6haloalkyl group which may have a branched structure, a cyclic structure,or an unsaturated bond, a phenyl group which may be substituted, or abenzyl group which may be substituted, or R² and R³ may be bonded toeach other to form a group having a cyclic structure); Z represents—OR¹, —SO_(p)R¹, —A(CH₂)_(n)QR¹, —NR²R³, —N(OR¹)R², —O(C═O)R¹, —O(C═O)OR¹, —O(C═O)SR¹, —O(C═O)NR²R³, or —O(C═S)NR²R³ (wherein R¹, R², and R³have the same definitions as described in relation to X and Y, each of Aand Q represents an oxygen atom or a sulfur atom, p is 0, 1, or 2, n is1 or 2), —OM (wherein M represents a hydrogen atom, an alkali metal, analkaline earth metal, or an organic base), or a halogen atom; and m isan integer between 0 and 4 inclusive.

[0039] (8) A triketone derivative according to (7), wherein Y representsa hydrogen atom or a methyl group.

[0040] (9) A triketone derivative according to (7), wherein Y representsa hydrogen atom.

[0041] (10) A triketone derivative according to any one of (7) to (9),wherein Z represents a halogen atom, —OR¹, —SO_(p)R¹, —A(CH₂)_(n)QR¹, or—N(OR¹)R².

[0042] (11) A triketone derivative according to any one of (1) to (10),wherein X represents a halogen atom or a methyl group.

[0043] (12) A herbicide containing a triketone derivative as recited inany one of (1) to (11) as an active ingredient.

[0044] (13) A herbicide for use in cultivation of a paddy rice plant,which herbicide contains a triketone derivative as recited in any one of(1) to (11) as an active ingredient.

BEST MODE FOR CARRYING OUT THE INVENTION

[0045] Hereafter, various modes for carrying out the present inventionwill be described.

[0046] I. The First Aspect of the Invention

[0047] The triketone derivative of the first aspect of the presentinvention (may be simply referred to as “the present invention”throughout section I) is represented by chemical formula [I-1]. Ofthese, triketone derivatives represented by formulas [I-2] and [I-3] arepreferred in that they provide a low level of chemical injury tocultivated plants and have an excellent weed-controlling effect.

[0048] When each of R¹ to R³ in formulas [I-1] to [I-4] represents aC1-C6 alkyl group which may have a branched structure, a cyclicstructure, or an unsaturated bond, examples of the alkyl group include amethyl group, an ethyl group, an n-propyl group, an i-propyl group, ann-butyl group, an i-butyl group, a sec-butyl group, a tert-butyl group,an n-pentyl group, an i-pentyl group, a sec-pentyl group, an n-hexylgroup, and an i-hexyl group. The ethyl group, propyl groups, and butylgroups may have an unsaturated bond, and the propyl groups, butylgroups, pentyl groups, and hexyl groups may be linear, branched, orcyclic. Of these, a methyl group and an ethyl group are preferred.

[0049] When each of R¹ to R³ in formulas [I-1] to [I-4] represents aC1-C6 haloalkyl group which may have a branched structure, a cyclicstructure, or an unsaturated bond, examples of the haloalkyl groupinclude the above-described alkyl groups in which some or all of thehydrogen atoms are substituted by a halogen atom such as a chlorineatom, a fluorine atom, a bromine atom, or an iodine atom. Specificexamples include a chloromethyl group, a difluoromethyl group, atrichloromethyl group, a trifluoromethyl group, a 2-chloroethyl group, a2-fluoroethyl group, a 3-chloropropyl group, and a 3-fluoropropyl group.Of these, a trifluoromethyl group and a trichloromethyl group arepreferred.

[0050] When each of R¹ to R³ in formulas [I-1] to [I-4] represents aphenyl group which may be substituted, examples of the phenyl groupinclude a phenyl group, a tolyl group, an m-chlorophenyl group, ap-methoxyphenyl group, a p-nitrophenyl group, and p-cyanophenyl group.When each of R¹ to R³ represents a benzyl group which may besubstituted, examples of the benzyl group include a benzyl group, anα-methylbenzyl group, an o-methylbenzyl group, an m-chlorobenzyl group,a p-methoxybenzyl group, a p-nitrobenzyl group, and a p-cyanobenzylgroup.

[0051] When each of X and Y in formulas [I-1] to [I-4] or Z in formula[I-4] represents an —OR¹, examples of the alkoxy group include a methoxygroup, an ethoxy group, an n-propoxy group, an i-propoxy group, ann-butoxy group, an i-butoxy group, a sec-butoxy group, a tert-butoxygroup, an n-pentyloxy group, an i-pentyloxy group, a sec-pentyloxygroup, an n-hexyloxy group, and an i-hexyloxy group. The propoxy groupsand butoxy groups may have an unsaturated bond and may be linear,branched, or cyclic. In the above-described alkoxy groups, some or allof the hydrogen atoms may be substituted by a halogen atom. Examples ofsuch haloalkoxy groups include a chloromethyloxy group, adifluoromethyloxy group, a trichloromethyloxy group, atrifluoromethyloxy group, a 2-chloroethyloxy group, a 2-fluoroethyloxygroup, a 3-chloropropyloxy group, and a 3-fluoropropyloxy group. Ofthese, a methoxy group, an ethoxy group, a difluoromethyloxy group, anda trifluoromethyloxy group are preferred.

[0052] When each of X and Y in formulas [I-1] to [I-4] represents an—SR¹ group, examples of the alkylthio group include a methylthio group,an ethylthio group, an n-propylthio group, an i-propylthio group, ann-butylthio group, an i-butylthio group, a sec-butylthio group, atert-butylthio group, an n-pentylthio group, an i-pentylthio group, ann-hexylthio group, and an i-hexylthio group. The propylthio groups andbutylthio groups may have an unsaturated bond and may be linear,branched, or cyclic. In the above-described alkylthio groups, some orall of the hydrogen atoms may be substituted by a halogen atom. Examplesof such haloalkylthio groups include a chloromethylthio group, adifluoromethylthio group, a trichloromethylthio group, atrifluoromethylthio group, a 2-chloroethylthio group, a2-fluoroethylthio group, a 3-chloropropylthio group, and a3-fluoropropylthio group. Of these, a methylthio group, an ethylthiogroup, and a trifluoromethylthio group are preferred.

[0053] Examples of the —SO₂R¹ group include a methylsulfonyl group, anethylsulfonyl group, an n-propylsulfonyl group, an i-propylsulfonylgroup, an n-butylsulfonyl group, an i-butylsulfonyl group, asec-butylsulfonyl group, and a tert-butylsulfonyl group. Of these, amethylsulfonyl group and an ethylsulfonyl group are preferred.

[0054] When each of X, Y, and Z in formulas [I-1] to [I-4] represents an—NR²R³ group, examples thereof include a methylamino group, adimethylamino group, an ethylamino group, a pyrrolidinyl group, and apiperidino group. Examples of the —N(OR¹) R² group include amethoxyamino group, a methoxymethylamino group, a benzyloxyamino group,and an allyloxyamino group.

[0055] Example of the —NHCOR¹ include —NHCOCH₃, —NHCOC₂H₅, —NHCOC₃H₇,and —NHCOC₄H₁₀.

[0056] R⁴ in formulas [I-1] and [I-3] represents a hydrogen atom or aC1-C6 alkyl group. Examples of the C1-C6 alkyl group include a methylgroup, an ethyl group, an n-propyl group, an i-propyl group, an n-butylgroup, an i-butyl group, a sec-butyl group, a tert-butyl group, ann-pentyl group, an i-pentyl group, a sec-pentyl group, an n-hexyl group,and an i-hexyl group. Of these, a hydrogen atom and a methyl group arepreferred, with a hydrogen atom being particularly preferred.

[0057] Examples of preferable X in formulas [I-1] to [I-4] include ahalogen atom, —R¹, —OR¹, and —SR¹, with a halogen atom and a methylgroup being particularly preferred. Examples of preferable Y in formulas[I-1] to [I-4] include a hydrogen atom, a halogen atom, and —R¹, with ahydrogen atom, a methyl group, and a fluorine atom being particularlypreferred.

[0058] The number “m” in formulas [I-1] to [I-4] is 0-4, preferably 0-2,particularly preferably 0.

[0059] When Z in formula [I-4] represents an —SOPR¹ group, examplesthereof include alkylsulfonyl groups such as a methylsulfonyl group, anethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, apentylsulfonyl group, and a hexylsulfonyl group; alkylsulfinyl groupssuch as a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinylgroup, a butylsulfinyl group, a pentylsulfinyl group, and ahexylsulfinyl group; and alkylthio groups such as a methylthio group, anethylthio group, a propylthio group, a butylthio group, a pentylthiogroup, and a hexylthio group.

[0060] Examples of M contained in the —OM group in formulas [I-1] to[I-3] and in formula [I-4] when Z represents an —OM group include ahydrogen atom; alkali metal atoms such as lithium, sodium, andpotassium; alkaline earth metal atoms such as magnesium, calcium, andbarium; organic bases such as trimethylamine, triethylamine, andaniline. Of these, a hydrogen atom is particularly preferred as M.

[0061] When Z in a triketone derivative represented by formula [I-4] isa hydroxy group, the derivative may be tautomers having the followingstructures:

[0062] wherein R, R⁴, X, Y, and m have the same definitions as describedin relation to formula [I-4]. The triketone derivative of the presentinvention encompasses all these tautomeric compounds and mixturesthereof.

[0063] A process for producing the triketone derivative of the presentinvention will next be described. First of all, an intermediate forproducing the triketone derivative of the present invention; i.e.,benzothiophene-2-carboxylic acid, is produced. For example, theintermediate can be effectively produced through the following steps.

[0064] (1) First Step:

[0065] In the first step, Compounds (a) and (b) are used in an amount of1 mol each to carry out the above reaction in the presence of 1 mol ormore of a base to thereby obtain Compound (c). Either of Compound (a) orCompound (b) may be used in an amount in excess of equimol with respectto the other.

[0066] Examples of the base which can be used in the reaction include analkali metal carbonate, an alkaline earth metal carbonate, and an alkalimetal hydroxide. Examples of a solvent which is inert to the reactionand used in the reaction include alcohols such as methanol and ethanol;halohydrocarbons such as chloroform and dichloromethane; hydrocarbonssuch as hexane and toluene; N,N dimethylformamide; and water. Thereaction is carried out in the temperature range of 0° C. to the boilingpoint of the employed solvent, with stirring until completion of thereaction.

[0067] Alternatively, the reaction may be carried out in a two-phasesystem in the presence of a quaternary ammonium salt. Furthermore,Compound (a) may be reacted with sodium hydrogensulfide or potassiumhydrogensulfide, and chloroacetic acid or bromoacetic acid, to therebyobtain Compound (c).

[0068] When the substituent X or Y in Compound (c) is a leaving group,the product may be obtained as a mixture. In this case, the product ispurified through a process such as distillation, recrystallization, orchromatographic purification, to thereby yield the target compound.

[0069] (2) Second Step:

[0070] In the second step, Compound (c) is cyclized to form Compound (d)as shown in the above reaction. The cyclization is carried out in thepresence of an acidic reagent in a catalyst amount or in an amount ofequimol or more. Examples of preferred acidic reagents includehydrochloric acid, sulfuric acid, phosphorus trichloride, phosphoruspentachloride, phosphorus oxychloride, polyphosphoric acid, acetic acid,acetic anhydride, trifluoromethanesulfonic acid/trifluoromethanesulfonic anhydride, and sulfuryl chloride. The reactionmay be carried out in the absence of a solvent. When a solvent isemployed, examples of preferred solvents include hexane,dichloromethane, 1,2-dichloroethane, chloroform, andN,N-dimethylformamide. The reaction is carried out in the temperaturerange of −20° C. to the boiling point of the employed solvent, withstirring until completion of the reaction.

[0071] Alternatively, Compound (c) is transformed into its acid halide,and the acid halide is reacted in the presence of a Lewis acid. In thiscase, the transformation is carried out by use of a halogenating agentsuch as oxalyl chloride or thionyl chloride in an amount of equimol ormore in the absence of a solvent or in the presence of a solvent such asmethylene chloride, 1,2-dichloroethane, or chloroform. The reaction iscarried out in the temperature range of room temperature to the boilingpoint of the employed solvent, with stirring until completion of thereaction. The subsequent reaction is carried out by use of a Lewis acidsuch as aluminum chloride, titanium tetrachloride, or tin tetrachloride.The reaction is carried out in the temperature range of −20° C. to theboiling point of the employed solvent, with stirring until completion ofthe reaction. When Y of Compound (d) is a hydrogen atom, the otherisomer may be intermingled with the product as an impurity. In such acase, the product is purified through a method as described above.

[0072] (3) Third Step:

[0073] In the third step, Compound (d) is reduced to form Compound (e)as shown in the above reaction. Examples of preferred reducing agentsused in the reduction include sodium borohydride and aluminumtriisopropoxide. Examples of preferred solvents include methanol,ethanol, water, dichloromethane, and toluene. The reduction is carriedout in the temperature range of −20° C. to the boiling point of anemployed solvent, with stirring until completion of the reaction.

[0074] (4) Fourth Step:

[0075] In the fourth step, Compound (e) is dehydrated to form Compound(f) as shown in the above reaction. The dehydration may be carried outin the presence of a catalyst amount of an acidic substance such ashydrochloric acid, sulfuric acid, p-toluenesulfonic acid, or Amberlist.In this case, a solvent such as benzene or toluene is preferred as areaction solvent, in that water formed during dehydration can be removedthrough azeotropic distillation. The formed water is adsorbed in anadsorbent such as a molecular sieve, or is removed through azeotropicdistillation with the solvent, to thereby accelerate dehydration. Whensuch an adsorbent is used, the dehydration is carried out in thetemperature range of room temperature to 50° C. with stirring untilcompletion of the reaction. Azeotropic distillation is carried outthrough refluxing with heat at the boiling point of the employed solventuntil the theoretical amount of water is removed.

[0076] (5) Fifth Step:

[0077] In the fifth step, Compound (f) is oxidized to form Compound (g)as shown in the above reaction. The oxidation is carried out in thepresence of an organic peroxide such as hydrogen peroxide orm-chloroperbenzoic acid in an amount of 2 mol or more. In this case, asolvent such as acetic acid or methylene chloride is preferred as areaction solvent. The oxidation is carried out in the temperature rangeof −20° C. to 100° C., with stirring until completion of the reaction.

[0078] (6) Sixth Step:

[0079] In the sixth step, Compound (g) is hydrogenated to form Compound(h) as shown in the above reaction. The hydrogenation is carried outunder similar conditions as employed for customary catalytichydrogenation. Examples of preferred catalysts includepalladium-on-active carbon, Raney nickel, and platinum oxide. In thiscase, a solvent such as tetrahydrofuran, methanol, ethanol, ethylacetate, or water is preferred as a reaction solvent. The hydrogenationis carried out in a hydrogen gas atmosphere, with or without pressure,and in the temperature range of room temperature to the boiling point ofthe employed solvent, with stirring until completion of the reaction.

[0080] (7) Seventh Step:

[0081] In the seventh step, Compound (h) is hydrolyzed to form Compound(i) as shown in the above reaction. The hydrogenation is carried out inthe presence of an alkali metal hydroxide in an amount of equimol ormore in a mixture of water and alcohol such as ethanol as a solvent. Thehydrolysis is carried out in the temperature range of room temperatureto the boiling point of the employed solvent, with stirring untilcompletion of the reaction.

[0082] The thus-obtained intermediate, benzothiophene-2-carboxylic acid,is used in the following reaction:

[0083] wherein R, R⁴, X, Y, and m have the same definitions as describedin relation to formula [I-1] to [I-4], to thereby produce triketonederivatives as represented by formula [I-1] to [I-3] and a triketonederivative as represented by formula [I-4] wherein Z represents ahydroxy group.

[0084] The intermediate, benzothiophene-2-carboxylic acid, istransformed into an acid halide thereof as described in relation to theabove-described cyclization. The thus-formed acid halide is reacted witha diketone in the presence of an organic base such as triethylamine at0-20° C. in an inert organic reaction solvent such as acetonitrile, andthe reaction mixture is allowed to react with stirring at roomtemperature in the presence of a catalyst amount of a cyanide-donor suchas acetone cyanohydrin.

[0085] Furthermore, the thus-obtained triketone derivatives representedby formula [I-1] to [I-3] and triketone derivative represented byformula [I-4] wherein Z represents a hydroxy group are reacted with acompound which can substitute some or all of the hydroxy groups inaccordance with reaction, e.g., reaction as described in Japanese PatentApplication Laid-Open (kokai) Nos. 62-298563, 62-242755, or 63-2947, tothereby produce substituted triketone derivatives represented by formula[I-1] to [I-3] and triketone derivative represented by formula [I-4]wherein Z represents a variety of substituents.

[0086] II. The Second Aspect of the Invention

[0087] The triketone derivative of the second aspect of the presentinvention (may be simply referred to as “the present invention”throughout section II) is represented by chemical formula [II-1]. Ofthese, triketone derivatives represented by formulas [II-2] and [II-3]are preferred. Furthermore, among the triketone derivatives representedby formulas [II-2] and [II-3], triketone derivatives represented byformulas [II-4] to [II-9] are more preferred in that they provide a lowlevel of chemical injury to cultivated plants and have an excellentweed-controlling effect.

[0088] In the triketone derivatives represented by formulas [II-1] to[II-9], the substituent represented by X is preferably a halogen atom,an alkyl group represented by —R¹, an alkoxy group represented by —OR¹,or an alkylthio group represented by —SR¹. In the triketone derivativerepresented by formula [II-10], the substituent Y represents a hydrogenatom or a variety of groups. Of these, a hydrogen atom and a methylgroup are preferred. In the triketone derivative represented by formula[II-10], the substituent X represents a variety of groups. Of these, ahalogen atom and a methyl group are preferred.

[0089] In the triketone derivative represented by formulas [II-1] to[II-10], each of the substituents Z and Z¹ represents a variety ofgroups. Of these, a halogen atom, and —OR¹, —SO_(p)R¹, —A(CH₂)_(n)QR¹,—NR²R³, and —N(OR¹)R² described below are preferred.

[0090] When each of R¹ to R³ in formulas [II-1] to [II-9] represents aC1-C6 alkyl group which may have a branched structure, a cyclicstructure, or an unsaturated bond, examples of the alkyl group include amethyl group, an ethyl group, an n-propyl group, an i-propyl group, ann-butyl group, an i-butyl group, a sec-butyl group, a tert-butyl group,an n-pentyl group, an i-pentyl group, a sec-pentyl group, an n-hexylgroup, and an i-hexyl group. The ethyl group, propyl groups, and butylgroups may have an unsaturated bond, and the propyl groups, butylgroups, pentyl groups, and hexyl groups may be linear, branched, orcyclic. Of these, a methyl group and an ethyl group are preferred.

[0091] When each of R¹ to R³ represents a C1-C6 haloalkyl group whichmay have a branched structure, a cyclic structure, or an unsaturatedbond, examples of the haloalkyl group include the above-described alkylgroups in which some or all of the hydrogen atoms are substituted by ahalogen atom such as a chlorine atom, a fluorine atom, a bromine atom,or an iodine atom. Specific examples include a chloromethyl group, adifluoromethyl group, a trichloromethyl group, a trifluoromethyl group,a 2-chloroethyl group, a 2-fluoroethyl group, a 3-chloropropyl group,and a 3-fluoropropyl group. Of these, a trifluoromethyl group ispreferred.

[0092] When each of R¹ to R³ represents a phenyl group which may besubstituted, examples of the phenyl group include a phenyl group, atolyl group, an m-chlorophenyl group, a p-methoxyphenyl group, ap-nitrophenyl group, and p-cyanophenyl group. When each of R¹ to R³represents a benzyl group which may be substituted, examples of thebenzyl group include a benzyl group, an a-methylbenzyl group, ano-methylbenzyl group, an m-chlorobenzyl group, a p-methoxybenzyl group,a p-nitrobenzyl group, and a p-cyanobenzyl group. Of these, a phenylgroup and a benzyl group are preferred. When each of X, Y, and Z¹ informulas [II-1] to [II-9] represents an —OR¹ group, examples of thealkoxy group include a methoxy group, an ethoxy group, propoxy groups,butoxy groups, pentyloxy groups, and hexyloxy groups. The propoxy groupsand butoxy groups may have an unsaturated bond and may be linear,branched, or cyclic. In the above-described alkoxy groups, some or allof the hydrogen atoms may be substituted by a halogen atom. Examples ofsuch haloalkoxy groups include a chloromethyloxy group, adifluoromethyloxy group, a trichloromethyloxy group, atrifluoromethyloxy group, a 2-chloroethyloxy group, a 2-fluoroethyloxygroup, a 3-chloropropyloxy group, and a 3-fluoropropyloxy group. Ofthese, a methoxy group, an ethoxy group, and an isopropoxy group arepreferred.

[0093] When each of X, Y, and Z¹ in formulas [II-1] to [II-9] representsan —SR¹ group, examples of the alkylthio group include a methylthiogroup, an ethylthio group, propylthio groups, butylthio groups,pentylthio groups, and hexylthio groups. The propylthio groups andbutylthio groups may have an unsaturated bond and may be linear,branched, or cyclic. In the above-described alkylthio groups, some orall of the hydrogen atoms may be substituted by a halogen atom. Examplesof such haloalkylthio groups include a chloromethylthio group, adifluoromethylthio group, a trichloromethylthio group, atrifluoromethylthio group, a 2-chloroethylthio group, a2-fluoroethylthio group, a 3-chloropropylthio group, and a3-fluoropropylthio group. Of these, a methylthio group, an ethylthiogroup, an i-propylthio group, and a t-butylthio group are preferred.

[0094] When each of X, Y, and Z¹ in formulas [II-1] to [II-9] representsan —SO_(p)R¹ group, examples of the —SO_(p)R¹ group includealkylsulfonyl groups such as a methylsulfonyl group, an ethylsulfonylgroup, propylsulfonyl groups, butylsulfonyl groups, pentylsulfonylgroups, and hexylsulfonyl groups; alkylsulfinyl groups such as amethylsulfinyl group, an ethylsulfinyl group, propylsulfinyl groups,butylsulfinyl groups, pentylsulfinyl groups, and hexylsulfinyl groups;and alkylthio groups such as a methylthio group, an ethylthio group,propylthio groups, butylthio groups, pentylthio groups, and hexylthiogroups. Of these, a methylsulfonyl group and an ethylsulfonyl group arepreferred. In addition, when each of X, Y, and Z¹ in the formulasrepresents an —NR²R³ group, examples thereof include a methylaminogroup, a dimethylamino group, an ethylamino group, a pyrrolidinyl group,and a piperidino group. When each of X, Y, and Z¹ in the formulasrepresents an —N(OR¹)R² group, examples of the —N(OR¹)R² group include amethoxyamino group, a methoxymethylamino group, a benzyloxyamino group,and an allyloxyamino group. Of these, a methoxymethylamino group ispreferred.

[0095] The number “q,” the number of the substituent X, is 1 or 2, with1 being preferred.

[0096] When Z in formula [II-10] represents an —O(C═O)R¹ group, examplesinclude an acetoxy group and a propionyloxy group.

[0097] When each of Z and Z¹ in formulas [II-1] to [II-10] represents an—O(C═O)OR¹ group, examples of the —O(C═O)OR¹ group include amethoxycarbonyloxy group, an ethoxycarbonyloxy group, and apropoxycarbonyloxy group. When each of Z and Z¹ in formulas [II-1] to[II-10] represents an —O(C═O)SR¹ group, examples of the —O(C═O)SR¹ groupinclude a methylthiocarbonyloxy group, an ethylthiocarbonyloxy group,and a propylthiocarbonyloxy group. When each of Z and Z¹ in formulas[II-1] to [II-10] represents an —O(C═O)NR¹R² group, examples of the—O(C═O)NR¹R² group include an N-methylcarbamoyl group, anN-ethylcarbamoyl group, and an N-dimethylcarbamoyl group. When each of Zand Z¹ in formulas [II-1] to [II-10] represents an —O(C═S)NR¹R² group,examples of the —O(C═S)NR¹R² group include an N-methylthiocarbamoylgroup, an N-ethylthiocarbamoyl group, and an N-dimethylthiocarbamoylgroup.

[0098] In these formulas, m is preferably 0-2, with 0 being particularlypreferred.

[0099] The triketone derivative represented by formula [II-1] may betautomers having the following structures:

[0100] wherein R, X, G, Z¹, m and q have the same definitions asdescribed in relation to formula [II-1]. The triketone derivative of thepresent invention encompasses all these tautomeric compounds andmixtures thereof.

[0101] Furthermore, examples of the optionally substitutedring-constituting atoms represented by G¹ to G⁴ in formulas [II-4] to[II-9], which are described as preferable examples of G, include anunsubstituted ring-constituting atom and a ring-constituting atom whichhas one or two substituents selected from the group consisting of amethyl group, an oxo group, a methoxy group, an isopropyloxy group, anda methoxyimino group. In the above formulas, i is preferably 2.

[0102] The process for producing the triketone derivative of the presentinvention will next be described. First of all, when G in formula [II-1]forms a 5-membered ring including two carbon atoms of the benzene ringadjacent to G, an intermediate for producing the triketone derivative ofthe present invention, i.e., benzothiophene-2-carboxylic acid, isproduced. For example, the intermediate can be effectively producedthrough the following steps.

[0103] (1) First Step:

[0104] In the first step, Compounds (a) and (b) are used in an amount of1 mol each to carry out the above reaction in the presence of 1 mol ormore of a base to thereby obtain Compound (c). Either of Compound (a) orCompound (b) may be used in an amount in excess of equimol with respectto the other.

[0105] Examples of the base which can be used in the reaction include analkali metal carbonate, an alkaline earth metal carbonate, and an alkalimetal hydroxide. Examples of a solvent which is inert to the reactionand used in the reaction include alcohols such as methanol and ethanol;halohydrocarbons such as chloroform and dichloromethane; hydrocarbonssuch as hexane and toluene; and water. The reaction is carried out inthe temperature range of 0° C. to the boiling point of the employedsolvent, with stirring until completion of reaction.

[0106] Alternatively, the reaction may be carried out in a two-phasesystem in the presence of a quaternary ammonium salt. Furthermore,Compound (a) may be reacted with sodium hydrogensulfide or potassiumhydrogensulfide and chloroacetic acid or bromoacetic acid, to therebyobtain Compound (c).

[0107] When the substituent X or Y in Compound (c) is a leaving group,the product may be obtained as a mixture. In this case, the product ispurified through a process such as distillation, recrystallization, orchromatographic purification, to thereby yield the target compound.

[0108] (2) Second Step:

[0109] In the second step, Compound (c) is cyclized to form Compound (d)as shown in the above reaction. The cyclization is carried out in thepresence of an acidic reagent in a catalyst amount or in an amount ofequimol or more. Examples of preferred acidic reagents includehydrochloric acid, sulfuric acid, phosphorus trichloride, phosphoruspentachloride, phosphorus oxychloride, polyphosphoric acid, acetic acid,acetic anhydride, trifluoromethanesulfonic acid,trifluoromethanesulfonic anhydride, and sulfuryl chloride. The reactionmay be carried out in the absence of a solvent. When a solvent is used,examples of preferred solvents include hexane, dichloromethane,1,2-dichloroethane chloroform, and N,N-dimethylformamide. The reactionis carried out in the temperature range of −20° C. to the boiling pointof the employed solvent, with stirring until completion of the reaction.

[0110] Alternatively, Compound (c) is transformed into its acidchloride, and the acid chloride is reacted in the presence of a Lewisacid. In this case, the transformation is carried out by use of ahalogenating agent such as oxalyl chloride or thionyl chloride in anamount of equimol or more in the absence of a solvent or in the presenceof a solvent such as methylene chloride, 1,2-dichloroethane, orchloroform. The reaction is carried out in the temperature range of roomtemperature to the boiling point of the employed solvent, with stirringuntil completion of the reaction. The subsequent reaction is carried outby use of a Lewis acid such as aluminum chloride, titaniumtetrachloride, or tin tetrachloride. The reaction is carried out in thetemperature range of −20° C. to the boiling point of the employedsolvent, with stirring until completion of the reaction. When Y ofCompound (d) is a hydrogen atom, the other isomer may be intermingledwith the product as an impurity. In such a case, the product is purifiedthrough a method as described above.

[0111] (3) Third Step:

[0112] In the third step, Compound (d) is reduced to form Compound (e)as shown in the above reaction. Examples of preferred reducing agentsused in the reduction include sodium borohydride and aluminumtriisopropoxide. Examples of preferred solvents include methanol,ethanol, water, dichloromethane, and toluene. The reduction is carriedout in the temperature range of −20° C. to the boiling point of theemployed solvent with stirring until completion of the reaction.

[0113] (4) Fourth Step:

[0114] In the fourth step, Compound (e) is dehydrated to form Compound(f) as shown in the above reaction. The dehydration may be carried outin the presence of a catalyst amount of an acidic substance such ashydrochloric acid, sulfuric acid, or p-toluenesulfonic acid. In thiscase, a solvent such as benzene or toluene is preferred as a reactionsolvent, in that water formed during dehydration can be removed throughazeotropic distillation. The formed water is adsorbed in an adsorbentsuch as a molecular sieve, or is removed through azeotropic distillationwith the solvent, to thereby accelerate dehydration. When such anadsorbent is used, the dehydration is carried out in the temperaturerange of room temperature to 50° C., with stirring until completion ofthe reaction. Azeotropic distillation is carried out through refluxingwith heat at the boiling point of the employed solvent by the time atheoretical amount of water is removed.

[0115] (5) Fifth Step:

[0116] In the fifth step, Compound (f) is oxidized to form Compound (g)as shown in the above reaction. The oxidation is carried out in thepresence of an organic peroxide such as hydrogen peroxide orm-chloroperbenzoic acid in an amount of 2 mol or more. In this case, asolvent such as acetic acid or methylene chloride is preferred as areaction solvent. The oxidation is carried out in the temperature rangeof −20° C. to 100° C., with stirring until completion of the reaction.

[0117] (6) Sixth Step:

[0118] In the sixth step, Compound (g) is hydrogenated to form Compound(h) as shown in the above reaction. The hydrogenation is carried outunder similar conditions as employed for customary catalytichydrogenation. Examples of preferred catalysts includepalladium-on-active carbon, Raney nickel, and platinum oxide. In thiscase, a solvent such as tetrahydrofuran, methanol, ethanol, ethylacetate, or water is preferred as a reaction solvent. The hydrogenationis carried out in a hydrogen gas atmosphere, with or without pressure,and in the temperature range of room temperature to the boiling point ofthe employed solvent, with stirring until completion of the reaction.

[0119] (7) Seventh Step:

[0120] In the seventh step, Compound (h) is hydrolyzed to form Compound(i) as shown in the above reaction. The hydrogenation is carried out inthe presence of an alkali metal hydroxide in an amount of equimol ormore in a mixture of water and alcohol such as ethanol as a solvent. Thehydrolysis is carried out in the temperature range of room temperatureto the boiling point of the employed solvent, with stirring untilcompletion of the reaction.

[0121] The thus-obtained intermediate is used in the following reaction:

[0122] wherein R, X, Y, and m have the same definitions as described inrelation to the above-described formulas, to thereby produce triketonederivatives as represented by the above-described formulas wherein Zrepresents a hydroxy group.

[0123] The intermediate carboxylic acid is transformed into an acidhalide thereof as described in relation to the above-describedcyclization. The thus-formed acid halide is reacted with a diketone inthe presence of an organic base such as triethylamine at 0-20° C. in aninert organic reaction solvent such as acetonitrile, and the reactionmixture is allowed to react with stirring at room temperature in thepresence of a catalyst amount of a cyanide-donor such as acetonecyanohydrin.

[0124] When G in the above formulas forms a 6- or 7-membered ringincluding two carbon atoms of the benzene ring adjacent to G, anintermediate for producing the triketone derivative can be producedthrough a method described in WO94/04524, WO94/08988, or WO97/03064.

[0125] Furthermore, either one of the thus-obtained triketonederivatives represented by the above formulas wherein Z represents ahydroxy group is reacted with a compound which can substitute some orall of the hydroxy groups in accordance with a reaction described, forexample, in Japanese Patent Application Laid-Open (kokai) Nos.62-298563, 62-242755, or 63-2947, to thereby produce substitutedtriketone derivatives represented by the above formulas wherein Zrepresents a variety of substituents.

[0126] III. Herbicides

[0127] The herbicides of the first and second aspects of the presentinvention (may be simply referred to as “the present invention”throughout section III) contain, as an active ingredient, triketonederivatives represented by formulas [I-1] to [I-4] in the first aspector represented by formulas as described above in the second aspect. Theherbicides are produced through mixing the triketone derivative with aliquid carrier such as a solvent or a solid carrier such as a mineralpowder, and are prepared into a variety of forms such aswater-dispersible powder, emulsion, powder, and granules for use. Duringpreparation of the herbicide, a surfactant is preferably added to theherbicide so as to impart properties such as an emulsifying property,dispersibility, and extendability to the herbicide.

[0128] When the herbicide of the present invention is used in the formof water-dispersible powder, the triketone derivative, a solid carrier,and a surfactant are typically mixed, in amounts of 5-55 wt. %, 40-93wt. %, and 2-5 wt. %, respectively, to thereby prepare a composition,which serves as a herbicide.

[0129] When the herbicide of the present invention is used in the formof emulsion, the triketone derivative, a solvent, and a surfactant aretypically mixed in amounts of 10-50 wt. %, 35-85 wt. %, and 5-15 wt. %,respectively, to thereby prepare a composition, which serves as aherbicide.

[0130] When the herbicide of the present invention is used in the formof powder, the triketone derivative, a solid carrier, and a surfactantare typically mixed in amounts of 1-15 wt. %, 80-97 wt. %, and 2-5 wt.%, respectively, to thereby prepare a composition, which serves as aherbicide.

[0131] When the herbicide of the present invention is used in the formof granules, the triketone derivative, a solid carrier, and a surfactantare typically admixed in amounts of 1-15 wt. %, 80-97 wt. %, and 2-5 wt.%, respectively, to thereby prepare a composition, which serves as aherbicide.

[0132] Examples of preferred solid carriers include oxides such asdiatomaceous earth and slaked lime; phosphates such as apatite; sulfatessuch as gypsum; and mineral micropowders such as talc, pyrophyllite,clay, kaolin, bentonite, acidic terra alba, white carbon, quartz powder,and silica stone powder.

[0133] Examples of preferred organic solvents include aromatichydrocarbons such as benzene, toluene, and xylene; chlorohydrocarbonssuch as o-chlorotoluene, trichloroethane, and trichloroethylnene;alcohols such as cyclohexanol, amyl alcohol, and ethylene glycol;ketones such as isophorone, cyclohexanone, andcyclohexenyl-cyclohexanone; ethers such as butyl cellosolve, diethylether, and methyl ethyl ether; esters such as isopropyl acetate, benzylacetate, and methyl phthalate; amides such as dimethylformamide; andmixtures thereof.

[0134] Examples of the surfactant which can be used in the inventioninclude anionic, nonionic, cationic, and ampholytic surfactants such asamino acid-type and betaine-type surfactants.

[0135] To the herbicide of the present invention, an ingredient having aweed-controlling activity may optionally be added other than thetriketone derivative represented by formulas [I-1] to [II-10]. Examplesof the compound contained in such an ingredient include diphenyl ether,triazine, urea, carbamate, thiocarbamate, acid anilide, pyrazole,phosphoric acid, sulfonylurea, and oxadiazone. These ingredients mayappropriately be used in combination.

[0136] Furthermore, additives such as a pesticide, a bactericide, aplant-growth-regulator, and a fertilizer may optionally be incorporatedinto the herbicide of the present invention.

[0137] The herbicide of the present invention is applied directly to aweed or to a field where the weed grows, before or after germination ofthe weed. The manner of application depends on the type of a cultivatedplant or the environment of use, and a form of application such asspraying, sprinkling, water sprinkling, or injecting may be employed.

[0138] Examples of the cultivated plant to which the herbicide isapplied include graminaceous plants such as rice, wheat, barley, corn,oat, and sorghum; broad-leaved crops such as soybean, cotton, beet,sunflower, and rape; fruit trees; vegetables such as fruit, root, andleaf vegetables; and turf grass.

[0139] Examples of paddy weeds to which the herbicide of the presentinvention applies include Alismataceae such as Alisma canaliculatum,Sagittaria trifolia, and Sagittaria pygmaea; Cyperaceae such as Cyperusdifformis, Cyperus serotinus, Scirpus juncoides, and Eleochariskuroguwai; Scrothulariaceae such as Lindernia pyxidaria; Pontenderiaceaesuch as Monochoria vaginalis; Potamogetonaceae such as Potamogetondistinctus; Lythraceae such as Rotala indica; and Gramineae such asEchinochloa crus-galli.

[0140] Examples of field weeds include broad-leaved weeds, graminaceousweeds, and cyperaceous weeds. Specific examples of broad-leaved weedsinclude Solanaceae such as Solanum nigrum and Datura stramonium;Malvaceae such as Abutilon theophrasti and Sida spinosa; Convolvulaceaesuch as Ipomoea purpurea; Amaranthaceae such as Amaranthus lividus;Compositae such as Xanthium strumarium, Ambrosia artemisifolia,Galinsoga ciliata, Cirsium arvense, Senecio Vulgaris, and Erigeronannus; Brassicaceae such as Rorippa indica, Sinapis arvensis, andCapsella bursa-pastoris; Polygonaceae such as Polygonum bulumei andPolygonum convolvulus; Portulacaceae such as Portulaca oleracea;Chenopodiaceae such as Chenopodium alubum, Chenopodium ficiolium, andKochia scoparia; Caryophyllaceae such as Stellaria media;Scrophulariaceae such as Veronica persica; Commelinaceae such asCommelina communis; Euphorbiaceae such as Lamium amplexicaule, Euphorbiasupina, and Euphorbia maculata; Rubiaceae such as Galium spurium, Galiumaparine, and Rubia akane; Vilaceae such as Viola arvensis; andLeguminosae such as Sesbania exaltata and Cassia obtusifolia. Specificexamples of Graminaceous weeds include Sorghum bicolor, Panicumdichotomiflorum, Sorghum haepense, Echinochloa crus-galli, Digitariaadscendes, Avena fatua, Eleusine indica, Setaria viridis, and Alopecurusaequalis. Specific examples of Cyperaceous weeds include Cyperusrotundus and Cyperus esculentus.

[0141] The present invention will next be described in more detail withreference to working examples and comparative examples.

EXAMPLES RELATED TO THE FIRST ASPECT OF THE INVENTION Example I-1 [1]Synthesis of4-chloro-5-oxycarbonyl-2,3-dihydrobenzothiophene-1,1-dioxide

[0142] (1) Synthesis of Ethyl 4-carboxymethylsulfenyl-2-chlorobenzoate

[0143] A mixture containing ethyl 2,4-dichlorobenzoate (10.0 g),potassium carbonate (9.44 g), dimethylformamide (50 ml), andmercaptoacetic acid (3.8 ml) was allowed to react with heat at 80° C.for 4 hours.

[0144] Next, the resultant reaction mixture was poured into ice waterand was subjected to extraction with ethyl acetate. The extract wasdried over sodium sulfate and filtered, then concentrated to therebyobtain a crude reaction product (12.3 g).

[0145] (2) Synthesis of4-chloro-5-ethoxycarbonyl-3-oxo-2,3-dihydrobenzothiophene

[0146] A mixture of ethyl 4-carboxymethylsulfenyl-2-chlorobenzoate (12.3g) obtained in (1), 1,2-dichloroethane (36 ml), and thionyl chloride(3.9 ml) was refluxed with heat over 1 hour.

[0147] Acid chloride obtained by concentration of the reaction mixturewas dissolved in dichloromethane (36 ml). Under cooling on ice, thesolution was added dropwise over 1 hour to a solution of aluminumchloride (14.3 g, 107 mmol) and dichloromethane (150 ml) prepared inadvance, after which reaction was continued for a further 2 hours atroom temperature.

[0148] The thus-obtained reaction mixture was poured into ice water andsubjected to extraction with dichloromethane. The extract was dried oversodium sulfate, filtered, and concentrated to thereby obtain a crudereaction product in the form of liver brown oil (12.3 g). Further, thecrude reaction product was purified by column chromatography to therebyobtain the compound of interest as brown oil (5.3 g, yield: 23%).

[0149] (3) Synthesis of4-chloro-5-ethoxycarbonyl-3-hydroxy-2,3-dihydrobenzothiophene

[0150] A solution comprising4-chloro-5-ethoxycarbonyl-3-oxo-2,3-dihydrobenzothiophene (5.3 g)obtained in (2), dichloromethane (25 ml), and ethanol (25 ml) was cooledin an ice-bath and sodium boron hydride (0.26 g) was added thereto,after which the solution was allowed to stand overnight.

[0151] Subsequently, the obtained reaction mixture was poured into icewater and subjected to extraction with dichloromethane. The extract wasdried over sodium sulfate and filtered to thereby obtain the compound ofinterest (5.3 g, yield: 98%).

[0152] (4) Synthesis of 4-chloro-5-ethoxycarbonylbenzothiophene

[0153] A mixture of4-chloro-5-ethoxycarbonyl-3-hydroxy-2,3-dihydrobenzothiophene (5.3 g)obtained in (3), toluene (50 ml), and p-toluene sulfate (0.2 g) wassubjected to azeotropic dehydration over 1 hour.

[0154] The resultant reaction mixture was diluted with toluene, washedwith a saturated solution of sodium hydrogencarbonate, and dried oversodium sulfate, followed by filtration and concentration to therebyobtain the compound of interest as brown oil (4.6 g, yield: 95%).

[0155] (5) Synthesis of4-chloro-5-ethoxycarbonylbenzothiophene-1,1-dioxide

[0156] A mixture containing 4-chloro-5-ethoxycarbonylbenzothiophene (4.6g) obtained in (4), acetic acid (30 ml), and a 30 wt. % aqueous solutionof hydrogen peroxide (5.4 ml) was allowed to react at 80° C. for 2 hourswith stirring.

[0157] After the reaction product was allowed to cool to roomtemperature, it was diluted with water and filtered to thereby obtain asolid. The solid was dried and purified by column chromatography tothereby obtain the compound of interest as colorless crystals (3.7 g,yield: 95%).

[0158] (6) Synthesis of4-chloro-5-ethoxycabonyl-2,3-dihydrobenzothiophene-1,1-dioxide

[0159] A mixture of 4-chloro-5-ethoxycarbonylbenzothiophene-1,1-dioxide(3.7 g) obtained in (5), tetrahydrofuran (40 ml), and 5%palladium/carbon was allowed to react in an atmosphere of hydrogen gasat ordinary temperature and pressure for 8 hours.

[0160] Subsequently, the resultant mixture was filtered and concentratedto thereby obtain the compound of interest as pale yellow oil (3.44 g,yield: 91%).

[0161] (7) Synthesis of4-chloro-5-oxycabonyl-2,3-dihydrobenzothiophene-1,1-dioxide

[0162] 4-Chloro-5-ethoxycarbonyl-2,3-dihydrobenzothiophene-1,1-dioxide(3.44 g) obtained in (6) was dissolved in ethanol (35 ml). To thesolution, a 20 wt. % aqueous solution of sodium hydroxide (5 ml) wasadded and the mixture was allowed to stand overnight.

[0163] Subsequently, the reaction mixture was concentrated and acidifiedby adding a 5 wt. % aqueous solution of hydrochloric acid, followed byfiltration and drying of the produced precipitate to thereby yield thecompound of interest as colorless crystals (2.6 g, yield: 84%).

[0164] A ¹H-NMR analysis (acetone-d⁶; TMS standard) of the thus-obtainedcolorless crystals showed peaks of 3.4-3.8 (m, 4H), 7.85 (1H, d), and8.06 (1H, d). Also, under infrared spectrum analysis, there wereobserved peaks at 3080 cm⁻¹, 3010 cm⁻¹, 1690 cm⁻¹, 1410 cm⁻¹, 1400 cm⁻¹,1310 cm⁻¹, 1290 cm⁻¹, 1250 cm⁻¹, 1190 cm⁻¹, and 1130 cm⁻¹. From theseresults, the compound was identified as4-chloro-5-oxycabonyl-2,3-dihydrobenzothiophene-1,1-dioxide, and itsmeasured melting point was 232-233° C.

[2] Synthesis of4-chloro-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. A-1]

[0165] As raw materials,4-chloro-5-oxycabonyl-2,3-dihydrobenzothiophene-1,1-dioxide (1.0 g)obtained in (1) and a suspension (4 ml) of thionyl chloride (0.54 g) in1,2-dichloroethane were reacted over 1 hour under reflux with heat.

[0166] From the obtained product, solvent was removed throughdistillation under reduced pressure, and the obtained acid chloride and1,3-cyclohexanedione (0.47 g) were dissolved in acetonitrile (10 ml)serving as a solvent. Thereafter, at room temperature, a solution oftriethylamine (0.82 g) in acetonitrile (5 ml) was added dropwisethereto.

[0167] After the mixture was stirred for 2 hours at room temperature,acetone cyanhydrin (0.01 g) was added thereto, followed by stirring for20 hours at room temperature.

[0168] To the resultant mixture, ethyl acetate was added and subjectedto extraction with saturated sodium carbonate. To an aqueous phase, 10%hydrochloric acid was added so as to adjust the pH of the phase to 1,and extraction with ethyl acetate was carried out. The thus-obtainedorganic phase was washed with water and aqueous saturated brine and thendried over anhydrous sodium sulfate. The solvent was removed from theproduct through distillation under reduced pressure to thereby obtainthe compound of interest,4-chloro-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide(1.24 g, yield: 90%).

[0169] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table I-1.

Example I-2 Synthesis of4-methyl-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No. A-2]

[0170] The target compound was obtained in the same manner as describedin Example I-1, except that4-methyl-5-oxycabonyl-2,3-dihydrobenzothiophene-1,1-dioxide was usedinstead of 4-chloro-5-oxycabonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0171] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table I-1.

Example I-3 Synthesis of 4-chloro-7-methyl-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide [Compound No. A-3]

[0172] The target compound was obtained in the same manner as describedin Example I-1, except that4-chloro-7-methyl-5-oxycarbonyl-2,3-dihydrobenzothiophene-1,1-dioxidewas used instead of4-chloro-5-oxycarbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0173] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table I-1.

Example I-4 Synthesis of4,7-dimethyl-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. A-4]

[0174] The target compound was obtained in the same manner as describedin Example I-1, except that4,7-dimethyl-5-oxycarbonyl-2,3-dihydrobenzothiophene-1,1-dioxide wasused instead of4-chloro-5-oxycarbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0175] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table I-1.

Example I-5 Synthesis of4-methoxy-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. A-5]

[0176] The target compound was obtained in the same manner as describedin Example I-1, except that4-methoxy-5-oxycarbonyl-2,3-dihydrobenzothiophene-1,1-dioxide was usedinstead of 4-chloro-5-oxycarbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0177] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table I-1.

Example I-6 Synthesis of4-methylthio-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. A-6]

[0178] The target compound was obtained in the same manner as describedin Example I-1, except that4-methylthio-5-oxycarbonyl-2,3-dihydrobenzothiophene-1,1-dioxide wasused instead of4-chloro-5-oxycarbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0179] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table I-1.

Example I-7 Synthesis of4-chloro-5-(4-methyl-1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. A-7]

[0180] The target compound was obtained in the same manner as describedin Example I-1, except that 4-methyl-1,3-cyclohexanedione was usedinstead of 1,3-cyclohexanedione.

[0181] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table I-1.

Example I-8 Synthesis of4-chloro-5-(4,4-dimethyl-1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. A-8]

[0182] The target compound was obtained in the same manner as describedin Example I-1, except that 4,4-dimethyl-1,3-cyclohexanedione was usedinstead of 1,3-cyclohexanedione.

[0183] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table I-1.

Example I-9 Synthesis of4-chloro-5-(5,5-dimethyl-1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. A-9]

[0184] The target compound was obtained in the same manner as describedin Example I-1, except that 5,5-dimethyl-1,3-cyclohexanedione was usedinstead of 1,3-cyclohexanedione.

[0185] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table I-1.

Example I-10 Synthesis of4-chloro-7-methyl-5-(5,5-dimethyl-1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. A-10]

[0186] The target compound was obtained in the same manner as describedin Example I-1, except that 5,5-dimethyl-1,3-cyclohexanedione and4-chloro-7-methyl-5-oxycarbonyl-2,3-dihydrobenzothiophene-1,1-dioxidewere used instead of 1,3-cyclohexanedione and4-chloro-5-oxycarbonyl-2,3-dihydrobenzothiophene-1,1-dioxide,respectively.

[0187] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table I-1.

Example I-11 Synthesis of4-chloro-7-methyl-5-(4,4-dimethyl-1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. A-11]

[0188] The target compound was obtained in the same manner as describedin Example I-1, except that 4,4-dimethyl-1,3-cyclohexanedione and4-chloro-7-methyl-5-oxycarbonyl-2,3-dihydrobenzothiophene-1,1-dioxidewere used instead of 1,3-cyclohexanedione and4-chloro-5-oxycarbonyl-2,3-dihydrobenzothiophene-1,1-dioxide,respectively.

[0189] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table I-1.

Example I-12 Synthesis of4-chloro-5-(5-methyl-1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. A-12]

[0190] The target compound was obtained in the same manner as describedin Example I-1, except that 5-methyl-1,3-cyclohexanedione was usedinstead of 1,3-cyclohexanedione.

[0191] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table I-1.

Example I-13 Synthesis of4-chloro-5-(4,4,6-trimethyl-1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. A-13]

[0192] The target compound was obtained in the same manner as describedin Example I-1, except that 4,4,6-trimethyl-1,3-cyclohexanedione wasused instead of 1,3-cyclohexanedione.

[0193] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table I-1.

Example I-14 Synthesis of4-chloro-5-(4,6-dimethyl-1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. A-14]

[0194] The target compound was obtained in the same manner as describedin Example I-1, except that 4,6-dimethyl-1,3-cyclohexanedione was usedinstead of 1,3-cyclohexanedione.

[0195] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table I-1.

Example I-15 Synthesis of4-chloro-5-(4,4,6,6-tetramethyl-1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. A-15]

[0196] The target compound was obtained in the same manner as describedin Example I-1, except that 4,4,6,6-tetramethyl-1,3-cyclohexanedione wasused instead of 1,3-cyclohexanedione.

[0197] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table I-1.

Example I-16 Synthesis of4-chloro-5-(4,5-dimethyl-1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. A-16]

[0198] The target compound was obtained in the same manner as describedin Example I-1, except that 4,5-dimethyl-1,3-cyclohexanedione was usedinstead of 1,3-cyclohexanedione.

[0199] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table I-1.

Example I-17 Synthesis of4-chloro-2-methyl-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. A-17]

[0200] The target compound was obtained in the same manner as describedin Example I-1, except that4-chlodro-2-methyl-5-oxycarbonyl-2,3-dihydrobenzothiophene-1,1-dioxidewas used instead of4-chloro-B-oxycarbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0201] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table I-1.

Example I-18 Synthesis of4-methoxy-2-methyl-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. A-18]

[0202] The target compound was obtained in the same manner as describedin Example I-1, except that4-methoxy-2-methyl-5-oxycarbonyl-2,3-dihydrobenzothiophene-1,1-dioxidewas used instead of4-chloro-5-oxycarbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0203] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table I-1.

Example I-19 Synthesis of a Sodium Salt of4-chloro-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. A-19]

[0204]4-Chloro-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide(0.1 g) obtained in the same manner as described in Example I-1 wasdissolved in tetrahydrofuran (8 ml) and the solution was added dropwiseto a suspension of sodium hydroxide (0.006 g) in tetrahydrofuran (2 ml).

[0205] After the mixture was stirred at room temperature for 25 hours,the solvent was removed through distillation under reduced pressure, andextraction with ethyl acetate was carried out. The extract was dried andcrystallized to thereby yield the compound of interest (0.08 g, yield:75%).

[0206] The chemical structure and the measured melting point of theobtained target compound are shown in Table I-1.

Example I-20 Synthesis of4-bromo-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. A-20]

[0207] The target compound was obtained in the same manner as describedin Example I-1, except that4-bromo-5-oxycarbonyl-2,3-dihydrobenzothiophene-1,1-dioxide was usedinstead of 4-chloro-5-oxycarbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0208] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table I-1.

Example I-21 Synthesis of4-cyano-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. A-21]

[0209] The target compound was obtained in the same manner as describedin Example I-1, except that4-cyano-5-oxycarbonyl-2,3-dihydrobenzothiophene-1,1-dioxide was usedinstead of 4-chloro-5-oxycarbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0210] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table I-1.

[0211] In the Table I-1, “(1)” to “(6)” indicates respectively asfollows.

[0212] (1) Example No.

[0213] (2) Compound No.

[0214] (3) Chemical structure

[0215] (4) NMR/ppm (CDCl₃, TMS standard)

[0216] (5) Infra Red Absorption (cm⁻¹)

[0217] (6) Property (mp: ° C.) TABLE I-1 (1) (2) (3) (4) (5) (6) I-1 A-1

1.9-2.3 (2H, m) 2.3-2.7 (2H, m) 2.6-3.0 (2H, m) 3.1-3.8 (4H, m) 7.32(1H, d) 7.69 (1H, d) 1675 1575 1550 1400 1295 1125 156.0-159.7 I-2 A-2

1.9-2.2 (2H, m) 2.20 (3H, s) 2.3-2.6 (2H, m) 2.7-3.0 (2H, m) 3.2-3.7(4H, m) 7.17 (1H, d) 7.60 (1H, d) 1670 1590 1300 1190 1120 203.8-204.3I-3 A-3

1.9-2.3 (2H, m) 2.4-2.6 (2H, m) 2.60 (3H, s) 2.7-2.9 (2H, m) 3.2-3.7(4H, m) 7.03 (1H, s) 1670 1560 1420 1300 1200 1135 213.0-214.7 I-4 A-4

1.9-2.2 (2H, m) 2.13 (3H, s) 2.3-2.6 (2H, m) 2.58 (3H, s) 2.7-3.0 (2H,m) 3.1-3.7 (4H, m) 6.90 (1H, s) 1675 1580 1425 1410 1295 1125218.5-220.7 I-5 A-5

1.9-2.3 (2H, m) 2.3-2.6 (2H, m) 2.7-2.9 (2H, m) 3.3-3.6 (4H, m) 3.83(3H, s) 7.23 (1H, d) 7.50 (1H, d) 1660 1590 1400 1300 1175 1115 syrupI-6 A-6

1.9-2.2 (2H, m) 2.25 (3H, s) 2.3-2.6 (2H, m) 2.7-3.0 (2H, m) 3.54 (4H,s) 7.21 (1H, d) 7.74 (1H, d) 1675 1570 1405 1300 1175 1125 195.2-196.1I-7 A-7

1.09 (3H, d) 1.5-3.0 (5H, m) 3.2-3.7 (4H, m) 7.26 (1H, d) 7.66 (1H, d)1680 1580 1565 1315 1195 1140 syrup I-8 A-8

1.0-1.5 (6H, m) 1.7-3.0 (4H, m) 3.2-3.7 (4H, m) 7.29 (1H, d) 7.70 (1H,d) 1600 1390 1305 1185 1170 1120 161.1-161.6 I-9 A-9

1.14 (6H, s) 2.3-2.7 (4H, m) 3.2-3.7 (4H, m) 7.30 (1H, d) 7.69 (1H, d)1670 1585 1555 1305 1195 1135 142.9-146.7 I-10 A-10

1.09 (6H, s) 2.32 (2H, s) 2.62 (3H, s) 2.68 (2H, s) 3.4-3.7 (4H, m) 7.05(1H, s) 2970 1660 1580 1290 1220 1190 syrup I-11 A-11

1.34 (6H, s) 1.8-2.0 (2H, m) 2.3-2.9 (2H, m) 2.63 (3H, s) 3.3-3.7 (4H,m) 7.03 (1H, s) 2970 1670 1580 1420 1380 1300 syrup I-12 A-12

1.13 (3H, d) 2.0-3.0 (5H, m) 3.3-3.7 (4H, m) 7.30 (1H, d) 7.70 2970 16701590 1400 1300 1180 syrup I-13 A-13

1.0-1.4 (9H., m) 1.6-2.0 (2H, m) 2.5-3.0 (1H, m) 3.3-3.7 (4H, m) 7.30(1H, d) 7.70 (1H, d) 2980 1730 1670 1580 1410 1310 syrup I-14 A-14

1.07 (3H, d) 1.09 (3H, d) 1.8-2.6 (3H, m) 2.8-3.2 (1H, m) 3.3-3.7 (4H,m) 7.30 (1H, d) 7.70 (1H, d) syrup I-15 A-15

1.19 (12H, d) 1.8-1.9 (2H, m) 3.3-3.6 (4H, m) 7.30 (1H, d) 7.70 (1H, d)syrup I-16 A-16

1.0-1.6 (6H, m) 2.0-2.8 (4H, m) 3.3-3.7 (4H, m) 7.30 (1H, d) 7.70 (1H,d) syrup I-17 A-17

1.56 (3H, d) 1.9-2.3 (2H, m) 2.3-2.6 (2H, m) 2.7-3.1 (3H, m) 3.4-3.8(2H, m) 7.28 (1H, d) 7.71 (1H, d) 1670 1575 1555 1450 1305 1140152.5-154.6 I-18 A-18

1.45 (3H, d) 2.0-3.1 (8H, m) 3.5-3.7 (1H, m) 3.79 (3H, s) 7.30 (1H, d)7.44 (1H, d) 1680 1580 1410 1300 1130 1010 syrup I-19 A-19

— — — I-20 A-20

1.9-2.3 (2H, m) 2.3-2.6 (2H, m) 2.7-3.0 (2H, m) 3.2-3.7 (4H, m) 7.24(1H, d) 7.74 (1H, d) 1670 1560 1395 1300 1195 1125 I-21 A-21

1.9-2.3 (2H, m) 2.3-3.0 (4H, m) 3.58 (4H, s) 7.51 (1H, d) 7.97 (1H, d)1660 1600 1580 1555 1300 1125 208.8-242.3

Example I-22

[0218] (1) Preparation of Herbicide

[0219] Talc (57 parts by weight) and bentonite (40 parts by weight),both serving as carriers, and sodium alkylbenzenesulfate (3 parts byweight) serving as a surfactant were homogeneously ground and mixed tothereby obtain a carrier for water-dispersible powder.

[0220] Subsequently, to the water-dispersible powder (90 parts byweight), the triketone derivative (compound No. A-1) produced in ExampleI-1 (10 parts by weight) was added, and the resultant mixture washomogeneously ground and mixed to thereby obtain a herbicide.

[0221] (2) Biological Tests of Herbicide

[0222] (i) Biological Test 1 (Soaking in Water/Treatment on the 3rd DayAfter Transplantation)

[0223] A Wagner pot (1/2000 are) was filled with paddy soil, and seedsof barnyard grass were planted on the surface layer of the soil, andfurther, rice seedlings grown to the 2.5-leaf stage were transplanted.

[0224] Subsequently, water was poured in the pot to a height of 3 cmabove the soil surface, and placed in a greenhouse where the temperaturewas maintained at 20-25° C., to thereby grow the plant under suitableconditions.

[0225] On the 3rd day after transplantation, the herbicide prepared in(1) above was applied to the plant in a predetermined amount. On the30th day after treatment with the herbicide, weed-killing ratio,herbicidal effect, and extent of chemical injury to paddy rice wereexamined.

[0226] (ii) Biological Test 2 (Soaking in Water/Treatment on the 10thDay After Transplantation)

[0227] A Wagner pot (1/2000 are) was filled with paddy soil, and seedsof barnyard grass were planted on the surface layer of the soil, andfurther, a rice seedling grown to the 2.5-leaf stage was transplanted.

[0228] Next, water was poured to the pot to a height of 3 cm above thesoil surface, and placed in a greenhouse where the temperature wasmaintained at 20-25° C., to thereby grow the plant under suitableconditions.

[0229] On the 10th day after transplantation, the herbicide prepared in(1) above was applied to the plant in a predetermined amount. On the30th day after treatment with the herbicide, weed-killing ratio,herbicidal effect, and extent of chemical injury to paddy rice wereexamined.

[0230] In Biological tests 1 and 2, herbicidal effect and extent ofchemical injury were evaluated according to the below-describedstandards.

[0231] 1) Weed-Killing Ratio

[0232] Weight of plants growing in the soil which had been treated withthe herbicide and weight of plants growing in the soil which had notbeen treated with the herbicide were measured, and weed-killing ratio(%) was calculated according to the following formula:

Weed-killing ratio (%)=[1−(Weight of plants growing in the soil whichhad been treated with the herbicide)/(weight of plants growing in thesoil which had not been treated with the herbicide)]×100

[0233] 2) Herbicidal Effect

[0234] Herbicidal effect was evaluated according to the followingcriteria. [Rating of [Herbicidal effect herbicidal effect] (weed-killingratio)] 0 less than 5% (almost no effect) 1  5% or more and less than20% 2 20% or more and less than 40% 3 40% or more and less than 70% 470% or more and less than 90% 5 90% or more (almost completely withered)

[0235] 3) Chemical Injury to Paddy Rice

[0236] Chemical injury to paddy rice was evaluated according to thefollowing criteria. [Rating of chemical injury to paddy rice] [Chemicalinjury to paddy rice] 0 No chemical injury to paddy rice was found. 1Chemical injury to paddy rice was hardly found. 2 slight chemical injuryto paddy rice was found. 3 Chemical injury to paddy rice was found. 4Chemical injury to paddy rice was predominantly found. 5 Paddy rice wasalmost completely withered.

[0237] The biological test results are shown in Table I-2.

Examples I-23 to I-40

[0238] (1) Preparation of Herbicides

[0239] Various herbicides were prepared in the same manner as describedin Example I-22 (1), except that the respective triketone derivativesobtained in Examples I-2 to I-21 were used instead of the triketonederivative used in Example I-22 (1).

[0240] (2) Biological Tests of Herbicide

[0241] Biological tests of herbicide were carried out in the same manneras described in Example I-22 (2), except that the respective herbicidesprepared in (1) were used instead of the herbicide prepared in ExampleI-22 (1).

[0242] The biological test results are shown in Table I-2.

Comparative Example I-1

[0243] (1) Preparation of Herbicide

[0244] A herbicide was prepared in the same manner as described inExample I-22 (1), except that a publicly known compound represented bythe following formula was used instead of the triketone derivative.

[0245] (2) Biological Tests of Herbicide

[0246] Biological tests of herbicide were carried out in the same manneras described in Example I-22 (2), except that a herbicide prepared in(1) was used instead of the herbicide prepared in Example I-22 (1).

[0247] The biological test results are shown in Table I-2.

Comparative Example I-2

[0248] (1) Preparation of Herbicide

[0249] A herbicide was prepared in the same manner as described inExample I-22 (1), except that a publicly known compound represented bythe following formula was used instead of the triketone derivative.

[0250] (2) Biological Tests of Herbicide

[0251] Biological tests of herbicide were carried out in the same manneras described in Example I-22 (2), except that a herbicide prepared in(1) was used instead of the herbicide prepared in Example 1-22 (1).

[0252] The biological test results are shown in Table I-2.

Comparative Example I-3

[0253] (1) Preparation of Herbicide

[0254] A herbicide was prepared in the same manner as described inExample I-22 (1), except that a publicly known compound represented bythe following formula was used instead of the triketone derivative.

[0255] (2) Biological Tests of Herbicide

[0256] Biological tests of herbicide were carried out in the same manneras described in Example I-22 (2), except that a herbicide prepared in(1) was used instead of the herbicide prepared in Example I-22 (1).

[0257] The biological test results are shown in Table I-2.

Comparative Example I-4

[0258] (1) Preparation of Herbicide

[0259] A herbicide was prepared in the same manner as described inExample I-22(1), except that a publicly known compound represented bythe following formula was used instead of the triketone derivative.

[0260] (2) Biological Tests of Herbicide

[0261] Biological tests of herbicide were carried out in the same manneras described in Example I-22 (2), except that a herbicide prepared in(1) was used instead of the herbicide prepared in Example I-22 (1).

[0262] The biological test results are shown in Table I-2(1) and (2).

[0263] In the Table I-2 (1) and (2), “(1)” to “(11)” indicatesrespectively as follows.

[0264] (1) Example No.

[0265] (2) Compound No.

[0266] (3) Dose (g/ha)

[0267] (4) Treatment performed 3 days after transplantation

[0268] (5) Treatment performed 10 days after transplantation

[0269] (6) Weed-killing effect

[0270] (7) Chemical injury

[0271] (8) Echinochloa crug-galli

[0272] (9) Scirups juncoides

[0273] (10) Transplanted paddy rice plant

[0274] (11) Comparative Example TABLE I-2 (1) (4) (5) (6) (7) (6) (1)(2) (3) (8) (9) (10) (8) (9) I- A-1 100 5 5 0 5 5 22 200 5 5 0 5 5 I-A-2 100 4 5 0 3 5 23 200 5 5 0 4 5 I- A-3 100 5 5 1 5 5 24 200 5 5 3 5 5I- A-4 100 4 5 0 4 5 25 200 5 5 1 4 5 I- A-5 100 3 4 0 3 4 26 200 5 5 04 4 I- A-6 100 5 5 1 4 4 27 200 5 5 3 5 5 I- A-7 100 5 5 1 4 5 28 200 55 2 5 5 I- A-8 100 5 5 1 5 5 29 200 5 5 3 5 5 I- A-9 100 5 5 1 5 5 30200 5 5 3 5 5 I- A-10 100 5 5 1 5 5 31 200 5 5 3 5 5 I- A-11 100 5 5 1 55 32 200 5 5 3 5 5 I- A-12 100 5 5 1 5 5 33 200 5 5 2 5 5 I- A-13 100 55 1 5 5 34 200 5 5 3 5 5 I- A-14 100 5 5 1 5 5 35 200 5 5 2 5 5 I- A-15100 5 5 1 5 5 36 200 5 5 3 5 5 I- A-16 100 5 5 1 5 5 37 200 5 5 3 5 5 I-A-17 100 3 4 0 3 4 38 200 4 5 1 4 4 I- A-18 100 3 4 0 2 4 39 200 4 4 1 34 I- A-19 100 5 5 0 5 5 40 200 5 5 1 5 5 I-41 A-20 100 5 5 0 5 5 200 5 50 5 5 I-42 A-21 100 5 5 0 5 5 200 5 5 0 5 5

[0275] TABLE I-2 (2) (4) (5) (6) (7) (6) (11) (3) (8) (9) (10) (8) (9)I-1 100 5 4 3 0 1 200 5 5 4 3 2 I-2 100 0 0 0 0 0 200 1 1 0 0 0 I-3 1004 3 3 3 2 200 5 4 4 5 3 I-4 100 3 3 2 1 1 200 5 3 4 2 2

THE SECOND ASPECT OF THE INVENTION Example II-1 [1] Synthesis of4-chloro-5-oxycarbonyl-2,3-dihydrobenzothiophene-1,1-dioxide

[0276] (1) Synthesis of Ethyl 4-carboxymethylsulfenyl-2-chlorobenzoate

[0277] A mixture containing ethyl 2,4-dichlorobenzoate (10.0 g),potassium carbonate (9.44 g), dimethylformamide (50 ml), andmercaptoacetic acid (3.8 ml) was allowed to react with heat at 80° C.for 4 hours.

[0278] Next, the resultant reaction mixture was poured into ice waterand was subjected to extraction with ethyl acetate. The extract wasdried over sodium sulfate and filtered, then concentrated to therebyobtain a crude reaction product (12.3 g).

[0279] (2) Synthesis of4-chloro-5-ethoxycarbonyl-3-oxo-2,3-dihydrobenzothiophene

[0280] A mixture of ethyl 4-carboxymethylsulfenyl-2-chlorobenzoate (12.3g) obtained in (1), 1,2-dichloroethane (36 ml), and thionyl chloride(3.9 ml) was refluxed with heat over 1 hour.

[0281] Acid chloride obtained by concentration of the reaction mixturewas dissolved in dichloromethane (36 ml). The solution was addeddropwise under cooling on ice over 1 hour to a solution of aluminumchloride (14.3 g, 107 mmol) and dichloromethane (150 ml) prepared inadvance, after which the reaction was continued for a further 2 hours atroom temperature.

[0282] The thus-obtained reaction mixture was poured into ice water andsubjected to extraction with dichloromethane. The extract was dried oversodium sulfate, filtered, and concentrated to thereby obtain a crudereaction product in the form of liver brown oil (12.3 g). Further, thecrude reaction product was purified by column chromatography to therebyobtain the compound of interest as brown oil (5.3 g, yield: 23%).

[0283] (3) Synthesis of4-chloro-5-ethoxycarbonyl-3-hydroxy-2,3-dihydrobenzothiophene

[0284] A solution comprising4-chloro-5-ethoxycarbonyl-3-oxo-2,3-dihydrobenzothiophene (5.3 g)obtained in (2), dichloromethane (25 ml), and ethanol (25 ml) was cooledin an ice-bath and sodium boron hydride (0.26 g) was added thereto,after which the solution was allowed to stand overnight.

[0285] Subsequently, the obtained reaction mixture was poured into icewater and subjected to extraction with dichloromethane. The extract wasdried over sodium sulfate and filtered to thereby obtain the compound ofinterest (5.3 g, yield: 98%).

[0286] (4) Synthesis of 4-chloro-5-ethoxycarbonylbenzothiophene

[0287] A mixture of4-chloro-5-ethoxycarbonyl-3-hydroxy-2,3-dihydrobenzothiophene (5.3 g)obtained in (3), toluene (50 ml), and p-toluene sulfate (0.2 g) wassubjected to azeotropic dehydration over 1 hour.

[0288] The resultant reaction mixture was diluted with toluene, washedwith a saturated solution of sodium hydrogencarbonate, and dried oversodium sulfate, followed by filtration and concentration to therebyobtain the compound of interest as brown oil (4.6 g, yield: 95%).

[0289] (5) Synthesis of4-chloro-5-ethoxycarbonylbenzothiophene-1,1-dioxide

[0290] A mixture containing 4-chloro-5-ethoxycarbonylbenzothiophene (4.6g) obtained in (4), acetic acid (30 ml), and a 30 wt. % aqueous solutionof hydrogen peroxide (5.4 ml) was allowed to react at 80° C. for 2 hourswith stirring.

[0291] After the reaction product was allowed to cool to roomtemperature, it was diluted with water and filtered to thereby obtain asolid. The solid was dried and purified by column chromatography tothereby obtain the compound of interest as colorless crystals (3.7 g,yield: 95%).

[0292] (6) Synthesis of4-chloro-5-ethoxycarbonyl-2,3-dihydrobenzothiophene-1,1-dioxide

[0293] A mixture of 4-chloro-5-ethoxycarbonylbenzothiophene-1,1-dioxide(3.7 g) obtained in (5), tetrahydrofuran (40 ml), and 5%palladium/carbon was allowed to react in an atmosphere of hydrogen gasat ordinary temperature and pressure for 8 hours.

[0294] Subsequently, the resultant mixture was filtered and concentratedto thereby obtain the compound of interest as pale yellow oil (3.44 g,yield: 91%).

[0295] (7) Synthesis of4-chloro-5-oxycarbonyl-2,3-dihydrobenzothiophene-1,1-dioxide

[0296] 4-Chloro-5-ethoxycarbonyl-2,3-dihydrobenzothiophene-1,1-dioxide(3.44 g) obtained in (6) was dissolved in ethanol (35 ml). To thesolution, a 20 wt. % aqueous solution of sodium hydroxide (5 ml) wasadded and the mixture was allowed to stand overnight.

[0297] Subsequently, the reaction mixture was concentrated and acidifiedby adding a 5 wt. % aqueous solution of hydrochloric acid, followed byfiltration and drying of the produced precipitate to thereby yield thecompound of interest as colorless crystals (2.6 g, yield: 84%).

[0298] A ¹H-NMR analysis (acetone-d⁶; TMS standard) of the thus-obtainedcolorless crystals showed peaks of 3.4-3.8 (m, 4H), 7.85 (1H, d), and8.06 (1H, d). Also, under infrared spectrum analysis, there wereobserved peaks at 3080 cm⁻¹, 3010 cm⁻¹, 1690 cm⁻¹, 1410 cm⁻¹1400 cm⁻¹,1310 cm⁻¹, 1290 cm⁻¹, 1250 cm⁻¹, 1190 cm⁻¹, and 1130 cm⁻¹. From theseresults, the compound was identified as4-chloro-5-oxycarbonyl-2,3-dihydrobenzothiophene-1,1-dioxide, and itsmeasured melting point was 232-233° C.

[2] Synthesis of4-chloro-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide

[0299] As raw materials,4-chloro-5-oxycarbonyl-2,3-dihydrobenzothiophene-1,1-dioxide (1.0 g)obtained in (7) and a suspension (4 ml) of thionyl chloride (0.54 g) in1,2-dichloroethane were reacted over 1 hour under reflux with heat.

[0300] The solvent was removed from the obtained product throughdistillation under reduced pressure, and the obtained acid chloride and1,3-cyclohexanedione (0.47 g) were dissolved in acetonitrile (10 ml)serving as a solvent. Thereafter, at room temperature, a solution oftriethylamine (0.82 g) in acetonitrile (5 ml) was added dropwisethereto.

[0301] After the mixture was stirred for 2 hours at room temperature,acetone cyanhydrin (0.01 g) was added thereto, followed by stirring for20 hours at room temperature.

[0302] To the resultant mixture, ethyl acetate was added and subjectedto extraction with saturated sodium carbonate. To an aqueous phase, 10%hydrochloric acid was added so as to adjust the pH of the phase to 1 andextraction with ethyl acetate was carried out. The thus-obtained organicphase was washed with water and aqueous saturated brine, and then driedover anhydrous sodium sulfate. The solvent was removed from the productthrough distillation under reduced pressure to thereby obtain thecompound of interest,4-chloro-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide(1.24 g, yield: 90%).

[3] Synthesis of4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-1]

[0303]4-Chloro-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide(1.00 g) obtained in [2] was dissolved in 1,2-dichloroethane (5 ml) andto the resultant solution, at room temperature, oxalyl chloride (0.56 g)and dimethylformamide (0.01 g) were added, followed by reaction over 1hour under reflux with heat.

[0304] Subsequently, from the resultant mixture, solvent was removedthrough distillation under reduced pressure, and the obtained crudeproduct was purified by column chromatography to thereby yield4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide(0.99 g, yield: 94%).

[0305] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-2 Synthesis of4-chloro-5-(3-ethylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-2]

[0306]4-Chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide(0.50 g) and ethanethiol (0.15 g) were dissolved in 1,2-dichloroethane(5 ml) and to the resultant solution, at room temperature, triethylamine(0.15 g) was added, followed by reaction for 5 hours with stirring.

[0307] After the resultant mixture was combined with water and subjectedto extraction with ethyl acetate, the organic phase was washed withaqueous saturated brine, and dried over anhydrous sodium sulfate.Further, the solvent was removed through distillation under reducedpressure, and the obtained crude product was purified by columnchromatography to thereby yield4-chloro-5-(3-ethylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide(0.50 g, yield: 83%).

[0308] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-3 Synthesis of4-chloro-5-(3-phenylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-3]

[0309] The target compound was prepared in the same manner as describedin Example II-2, except that benzenethiol was used instead ofethanethiol.

[0310] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-4 Synthesis of4-chloro-7-methyl-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-4]

[0311] The target compound was prepared in the same manner as describedin Example II-1, except that4-chloro-7-methyl-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxidewas used instead of4-chloro-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0312] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-5 Synthesis of4-chloro-7-methyl-5-(3-phenylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-5]

[0313] The target compound was prepared in the same manner as describedin Example II-2, except that4-chloro-7-methyl-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxideand benzenethiol were used instead of4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxideand ethanethiol, respectively.

[0314] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-6 Synthesis of4-chloro-5-(3-bromo-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-6]

[0315] The target compound was prepared in the same manner as describedin Example II-1, except that oxalyl bromide was used instead of oxalylchloride.

[0316] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-7 Synthesis of4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-7]

[0317] The target compound was prepared in the same manner as describedin Example II-2, except that methanethiol was used instead ofethanethiol.

[0318] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-8 Synthesis of4-chloro-5-[3-(3-propyl)thio-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-8]

[0319] The target compound was prepared in the same manner as describedin Example II-2, except that 1-propanethiol was used instead ofethanethiol.

[0320] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-9 Synthesis of4-chloro-5-(3-isopropylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-9]

[0321] The target compound was prepared in the same manner as describedin Example II-2, except that 2-propanethiol was used instead ofethanethiol.

[0322] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-10 Synthesis of4-chloro-5-[3-(4-butyl)thio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-10]

[0323] The target compound was prepared in the same manner as describedin Example II-2, except that 1-butanethiol was used instead ofethanethiol.

[0324] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-11 Synthesis of4-chloro-5-(3-benzylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-11]

[0325] The target compound was prepared in the same manner as describedin Example II-2, except that benzylthiol was used instead ofethanethiol.

[0326] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-12 Synthesis of4-chloro-5-[3-(N-methoxymethyl)amino-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-12]

[0327] As raw materials,4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide(0.50 g) and N,O-dimethylhydroxylamine hydrochloride (0.14 g) weredissolved in 1,2-dichloroethane (5 ml) and to the resultant solution,triethylamine (0.15 g) was added, followed by stirring for 5 hours tothereby react the solution.

[0328] After the resultant mixture was combined with water, and thensubjected to extraction with ethyl acetate, the extract was washed withaqueous saturated brine and dried over anhydrous sodium sulfate.Further, the solvent was evaporated under reduced pressure, and theobtained crude product was purified by column chromatography to therebyyield4-chloro-5-[3-(N-methoxymethyl)amino-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide(0.43 g, yield: 80%).

[0329] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-13 Synthesis of4-chloro-5-(3-dimethylamino-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-13]

[0330] The target compound was prepared in the same manner as describedin Example II-12, except that dimethylamine hydrochloride was usedinstead of N,O-dimethylhydroxylamine hydrochloride.

[0331] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-14 Synthesis of4-chloro-5-[3-(4-methylphenyl)thio-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-14]

[0332] The target compound was prepared in the same manner as describedin Example II-2, except that 4-methylbenzenethiol was used instead ofethanethiol.

[0333] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-15 Synthesis of4-chloro-5-[3-(3-methylphenyl)thio-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-15]

[0334] The target compound was prepared in the same manner as describedin Example II-2, except that 3-methylbenzenethiol was used instead ofethanethiol.

[0335] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-16 Synthesis of4-chloro-5-[3-(2-methylphenyl)thio-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-16]

[0336] The target compound was prepared in the same manner as describedin Example II-2, except that 2-methylbenzenethiol was used instead ofethanethiol.

[0337] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-17 Synthesis of4-chloro-5-[3-(2-chlorophenyl)thio-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-17]

[0338] The target compound was prepared in the same manner as describedin Example II-2, except that 2-chlorobenzenethiol was used instead ofethanethiol.

[0339] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-18 Synthesis of4-chloro-5-[3-(2-isopropylphenyl)thio-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-18]

[0340] The target compound was prepared in the same manner as describedin Example II-2, except that 2-(2-propyl)benzenethiol was used insteadof ethanethiol.

[0341] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-19 Synthesis of4-chloro-5-[3-(2-methoxycarbonylphenyl)thio-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-19]

[0342] The target compound was prepared in the same manner as describedin Example II-2, except that 2-methoxycarbonylbenzenethiol was usedinstead of ethanethiol.

[0343] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-20 Synthesis of4-chloro-5-[3-(4-methoxyphenyl)thio-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-20]

[0344] The target compound was prepared in the same manner as describedin Example II-2, except that 4-methoxybenzenethiol was used instead ofethanethiol.

[0345] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-21 Synthesis of4-chloro-5-[3-(4-bromophenyl)thio-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-21]

[0346] The target compound was prepared in the same manner as describedin Example II-2, except that 4-bromobenzenethiol was used instead ofethanethiol.

[0347] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-22 Synthesis of4-chloro-5-[3-(3-propenyl)thio-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-22]

[0348] The target compound was prepared in the same manner as describedin Example II-2, except that 3-propenylthiol was used instead ofethanethiol.

[0349] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-23 Synthesis of4-chloro-5-[3-(2-methyl-2-propyl)thio-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-23]

[0350] The target compound was prepared in the same manner as describedin Example II-2, except that 2-(2-methylpropane)thiol was used insteadof ethanethiol.

[0351] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-24 Synthesis of4-chloro-5-(3-methylsulfonyl-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzdthiophene-1,1-dioxide[Compound No. B-24]

[0352]4-Chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide(0.80 g) was dissolved in dichloromethane (8 ml) and to the resultantsolution, m-chlorobenzoic acid (1.0 g) was added at room temperature,followed by allowing to stand overnight.

[0353] The resultant mixture was diluted with methylene chloride andfiltered. The filtrate was washed with a 5% aqueous solution of sodiumsulfite, a 5% aqueous solution of potassium carbonate, and aqueoussaturated brine, and dried over anhydrous sodium sulfate. After thefiltration of the drying agent, the filtered was concentrated to therebyobtain4-chloro-5-(3-methylsulfonyl-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide(0.76 g, yield: 87%).

[0354] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-25 Synthesis of4-chloro-5-(3-chloro-5-methyl-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-25]

[0355] The target compound was prepared in the same manner as describedin Example II-1, except that4-chloro-5-(5-methyl-1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxidewas used instead of4-chloro-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0356] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-26 Synthesis of4-chloro-5-(3-phenylthio-5-methyl-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-26]

[0357] The target compound was prepared in the same manner as describedin Example II-2, except that4-chloro-5-(3-chloro-5-methyl-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxideand benzenethiol were used instead of4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxideand ethanethiol, respectively.

[0358] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-27 Synthesis of4-chloro-5-(3-ethylsulfonyl-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-27]

[0359] The target compound was prepared in the same manner as describedin Example II-24, except that4-chloro-5-(3-ethylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxidewas used instead of4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0360] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-28 Synthesis of4-chloro-5-[3-(3-propyl)sulfonyl-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-28]

[0361] The target compound was prepared in the same manner as describedin Example II-24, except that4-chloro-5-[3-(3-propyl)thio-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxidewas used instead of4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0362] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-29 Synthesis of4-chloro-5-(3-isopropylsulfonyl-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-29]

[0363] The target compound was prepared in the same manner as describedin Example II-24, except that4-chloro-5-(3-isopropylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxidewas used instead of4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0364] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-30 Synthesis of4-chloro-5-[3-(4-butyl)sulfonyl-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-30]

[0365] The target compound was prepared in the same manner as describedin Example II-24, except that4-chloro-5-[3-(4-butyl)thio-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxidewas used instead of4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0366] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-31 Synthesis of4-chloro-5-(3-phenylsulfonyl-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-31]

[0367] The target compound was prepared in the same manner as describedin Example II-24, except that4-chloro-5-(3-phenylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxidewas used instead of4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0368] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-32 Synthesis of4-chloro-5-[3-(2-methylphenyl)sulfonyl-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-32]

[0369] The target compound was prepared in the same manner as describedin Example II-24, except that4-chloro-5-[3-(2-methylphenyl)thio-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxidewas used instead of4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0370] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-33 Synthesis of4-chloro-5-[3-(3-methylphenyl)sulfonyl-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-33]

[0371] The target compound was prepared in the same manner as describedin Example II-24, except that4-chloro-5-[3-(3-methylphenyl)thio-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxidewas used instead of4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0372] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-34 Synthesis of4-chloro-5-[3-(4-methylphenyl)sulfonyl-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-34]

[0373] The target compound was prepared in the same manner as describedin Example II-24, except that4-chloro-5-[3-(4-methylphenyl)thio-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxidewas used instead of4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0374] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-35 Synthesis of4-chloro-5-[3-(2-chlorophenyl)sulfonyl-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-35]

[0375] The target compound was prepared in the same manner as describedin Example II-24, except that4-chloro-5-[3-(2-chlorophenyl)thio-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxidewas used instead of4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0376] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-36 Synthesis of4-chloro-5-[3-(2-isopropylphenyl)sulfonyl-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-36]

[0377] The target compound was prepared in the same manner as describedin Example II-24, except that4-chloro-5-[3-(2-isopropylphenyl)thio-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxidewas used instead of4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0378] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-37 Synthesis of4-chloro-5-[3-(4-methoxyphenyl)sulfonyl-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-37]

[0379] The target compound was prepared in the same manner as describedin Example II-24, except that4-chloro-5-[3-(4-methoxyphenyl)thio-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxidewas used instead of4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0380] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-38 Synthesis of4-chloro-5-[3-(3-propenyl)sulfonyl-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-38]

[0381] The target compound was prepared in the same manner as describedin Example II-24, except that4-chloro-5-[3-(3-propenyl)thio-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxidewas used instead of4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0382] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-39 Synthesis of4-chloro-5-[3-(2-methyl-2-propyl)sulfonyl-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-39]

[0383] The target compound was prepared in the same manner as describedin Example II-24, except that4-chloro-5-[3-(2-methyl-2-propyl)thio-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxidewas used instead of4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0384] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-40 Synthesis of4-chloro-5-(3-benzylsulfonyl-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-40]

[0385] The target compound was prepared in the same manner as describedin Example II-24, except that4-chloro-5-(3-benzylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxidewas used instead of4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0386] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-41 Synthesis of4-chloro-5-[3-(4-hydroxyphenyl)thio-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-41]

[0387] The target compound was prepared in the same manner as describedin Example II-2, except that 4-hydroxybenzenethiol was used instead ofethanethiol.

[0388] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-42 Synthesis of4-chloro-5-[3-(4-bromophenyl)sulfonyl-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-42]

[0389] The target compound was prepared in the same manner as describedin Example II-24, except that4-chloro-5-[3-(4-bromophenyl)thio-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxidewas used instead of4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0390] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-43 Synthesis of4-chloro-5-[3-(4-hydroxyphenyl)sulfonyl-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-43]

[0391] The target compound was prepared in the same manner as describedin Example II-24, except that4-chloro-5-[3-(4-hydroxyphenyl)thio-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxidewas used instead of4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0392] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-44 Synthesis of4-chloro-5-[3-(2-methoxycarbonylphenyl)sulfonyl-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-44]

[0393] The target compound was prepared in the same manner as describedin Example II-24, except that4-chloro-5-[3-(2-methoxycarbonylphenyl)thio-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxidewas used instead of4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0394] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-45 Synthesis of4-chloro-5-[3-(4-acetylphenyl)thio-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-45]

[0395] The target compound was prepared in the same manner as describedin Example II-2, except that 4-acetylbenzenethiol was used instead ofethanethiol.

[0396] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-46 Synthesis of4-chloro-5-[3-(4-acetylphenyl)sulfonyl-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-46]

[0397] The target compound was prepared in the same manner as describedin Example II-24, except that4-chloro-5-[3-(4-acetylphenyl)thio-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxidewas used instead of4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0398] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table 11-1.

Example II-47 Synthesis of4-methyl-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-47]

[0399] The target compound was prepared in the same manner as describedin Example II-1, except that⁴-methyl-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxidewas used instead of4-chloro-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0400] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-48 Synthesis of4-chloro-5-[3-(2-hydroxyphenyl)thio-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-48]

[0401] The target compound was prepared in the same manner as describedin Example II-2, except that 2-hydroxybenzenethiol was used instead ofethanethiol.

[0402] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-49 Synthesis of4-chloro-5-[3-(2-hydroxyphenyl)sulfonyl-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-49]

[0403] The target compound was prepared in the same manner as describedin Example II-24, except that4-chloro-5-[3-(2-hydroxyphenyl)thio-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxidewas used instead of4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0404] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-50 Synthesis of4-methyl-5-(3-ethoxy-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-50]

[0405]4-Chloro-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide(1.7 g) was dissolved in methylene chloride (17 ml). Diethylaminosulfatetrifluoride (1.03 ml) was added to the resultant solution under coolingwith ice, followed by reaction with stirring for 1 hour at roomtemperature. To the resultant reaction mixture, ethanol (2 ml) wasadded, and reaction was allowed to proceed for one hour with stirring.

[0406] The resultant mixture was diluted with methylene chloride, washedwith aqueous saturated sodium bicarbonate solution, and dried overanhydrous sodium sulfate. After the desiccant was removed throughfiltration and the solvent was evaporated, the crude product wasrecrystallized from methanol to thereby obtain4-methyl-5-(3-ethoxy-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide(0.15 g, yield: 59%).

[0407] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-51 Synthesis of4-methyl-5-(3-isopropyloxy-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-51]

[0408] The target compound was prepared in the same manner as describedin Example II-50, except that isopropanol was used instead of ethanol.

[0409] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-52 Synthesis of4-methyl-5-(3-methoxy-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-52]

[0410] The target compound was prepared in the same manner as describedin Example II-50, except that methanol was used instead of ethanol.

[0411] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-53 Synthesis of4-chloro-5-[3-(2-methoxyethoxy)-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-53]

[0412] The target compound was prepared in the same manner as describedin Example II-50, except that 2-methoxyethanol was used instead ofethanol.

[0413] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-54 Synthesis of4-methoxyimino-5,8-dimethyl-6-(3-chloro-1-oxocyclohexan-2-yl)carbonylthiochroman-1,1-1,1-dioxide[Compound No. B-54]

[0414] The target compound was prepared in the same manner as describedin Example II-1, except that4-methoxyimino-5,8-dimethyl-6-(1,3-dioxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxidewas used instead of4-chloro-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0415] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-55 Synthesis of4-methoxyimino-5,8-dimethyl-6-(3-dimethylamino-1-oxocyclohexan-2-yl)carbonylthiochroman-1,1-1,1-dioxide[Compound No. B-55]

[0416] The target compound was prepared in the same manner as describedin Example II-12, except that4-methoxyimino-5,8-dimethyl-6-(3-chloro-1-oxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxideand dimethylamine hydrochloride were used instead of4-chloro-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxideand N,O-dimethylhydroxylamine hydrochloride, respectively.

[0417] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-56 Synthesis of4-methoxyimino-5,8-dimethyl-6-(3-methylthio-1-oxocyclohexan-2-yl)carbonylthiochroman-1,1-1,1-dioxide[Compound No. B-56]

[0418] The target compound was prepared in the same manner as describedin Example II-2, except that4-methoxyimino-5,8-dimethyl-6-(3-chloro-1-oxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxideand methanethiol were used instead of4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxideand ethanethiol, respectively.

[0419] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-57 Synthesis of4-methoxyimino-5,8-dimethyl-6-[3-(N-methoxymethyl)amino-1-oxocyclohexan-2-yl]carbonylthiochroman-1,1-1,1-dioxide[Compound No. B-57]

[0420] The target compound was prepared in the same manner as describedin Example II-12, except that4-methoxyimino-5,8-dimethyl-6-(3-chloro-1-oxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxidewas used instead of4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0421] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-58 Synthesis of4-methoxyimino-5,8-dimethyl-6-[3-(4-methylphenyl)amino-1-oxocyclohexan-2-yl]carbonylthiochroman-1,1-1,1-dioxide[Compound No. B-58]

[0422] The target compound was prepared in the same manner as describedin Example II-12, except that4-methoxyimino-5,8-dimethyl-6-(3-chloro-1-oxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxideand 4-methylphenylamine were used instead of4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxideand N,O-dimethylhydroxylamine, respectively.

[0423] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and-measured melting point of the compound are shownin Table II-1.

Example II-59 Synthesis of4-methoxyimino-5,8-dimethyl-6-[3-(4-methylphenyl)thio-1-oxocyclohexan-2-yl]carbonylthiochroman-1,1-1,1-dioxide[Compound No. B-59]

[0424] The target compound was prepared in the same manner as describedin Example II-2, except that4-methoxyimino-5,8-dimethyl-6-(3-chloro-1-oxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxideand 4-methylbenzenethiol were used instead of4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxideand ethanethiol, respectively.

[0425] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-60 Synthesis of4-methoxyimino-5,8-dimethyl-6-[3-(4-methylphenyl)sulfonyl-1-oxocyclohexan-2-yl]carbonylthiochroman-1,1-1,1-dioxide[Compound No. B-60]

[0426] The target compound was prepared in the same manner as describedin Example II-24, except that4-methoxyimino-5,8-dimethyl-6-[3-(4-methylphenyl)thio-1-oxocyclohexan-2-yl]carbonylthiochroman-1,1-dioxidewas used instead of4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0427] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-61 Synthesis of4-methoxyimino-5,8-dimethyl-6-[3-(3-propyl)thio-1-oxocyclohexan-2-yl)carbonylthiochroman-1,1-1,1-dioxide[Compound No. B-61]

[0428] The target compound was prepared in the same manner as describedin Example II-2, except that4-methoxyimino-5,8-dimethyl-6-(3-chloro-1-oxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxideand 3-propanethiol were used instead of4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxideand ethanethiol, respectively.

[0429] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-62 Synthesis of4-methoxyimino-5,8-dimethyl-6-[3-(3-propyl)sulfonyl-1-oxocyclohexan-2-yl]carbonylthiochroman-1,1-1,1-dioxide[Compound No. B-62]

[0430] The target compound was prepared in the same manner as describedin Example II-24, except that4-methoxyimino-5,8-dimethyl-6-[3-(3-propyl)thio-1-oxocyclohexan-2-yl]carbonylthiochroman-1,1-dioxidewas used instead of4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0431] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-63 Synthesis of3,3,5-trimethyl-6-(3-chloro-1-oxocyclohexan-2-yl)carbonylthiochroman-4-one-1,1-dioxide[Compound No. B-63]

[0432] The target compound was prepared in the same manner as describedin Example II-1 except that3,3,5-trimethyl-6-(1,3-dioxocyclohexan-2-yl)carbonylthiochroman-4-one-1,1-dioxidewas used instead of4-chloro-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0433] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-64 Synthesis of3,3,5-trimethyl-6-[3-(4-chloro)thio-1-oxocyclohexan-2-yl]carbonylthiochroman-4-one-1,1-dioxide[Compound No. B-64]

[0434] The target compound was prepared in the same manner as describedin Example II-2 except that3,3,5-trimethyl-6-(3-chloro-1-oxocyclohexan-2-yl)carbonylthiochroman-4-one-1,1-dioxideand 4-chlorobenzenethiol were used instead of4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxideand ethanethiol, respectively.

[0435] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting

Example II-65 Synthesis of4-methoxyimino-5,6-dimethyl-6-(3-(4-chlorophenyl)sulfonyl-1-oxocyclohexan-2-yl]carbonylthiochroman-4-one-1,1-dioxide[Compound No. B-65]

[0436] The target compound was prepared in the same manner as describedin Example II-24 except that4-methoxyimino-5,8-dimethyl-6-[3-(4-chlorophenyl)thio-1-oxocyclohexan-2-yl]carbonylthiochroman-4-one-1,1-dioxidewas used instead of4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0437] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-66 Synthesis of4-(2-propyl)oxy-5,8-dimethyl-6-(3-chloro-1-oxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxide[Compound No. B-66]

[0438] The target compound was prepared in the same manner as describedin Example II-1 except that4-(2-propyl)oxy-5,8-dimethyl-6-(1,3-dioxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxidewas used instead of4-chloro-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0439] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-67 Synthesis of4-(2-propyl)oxy-5,8-dimethyl-6-(3-methylthio-1-oxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxide[Compound No. B-67]

[0440] The target compound was prepared in the same manner as describedin Example II-2 except that4-(2-propyl)oxy-5,8-dimethyl-6-(3-chloro-1-oxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxideand methanethiol were used instead of4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxideand ethanethiol, respectively.

[0441] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-68 Synthesis of4-(2-propyl)oxy-5,8-dimethyl-6-(3-phenylthio-1-oxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxide[Compound No. B-68]

[0442] The target compound was prepared in the same manner as describedin Example II-2 except that4-(2-propyl)oxy-5,8-dimethyl-6-(3-chloro-1-oxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxideand benzenethiol were used instead of4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxideand ethanethiol, respectively.

[0443] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-69 Synthesis of4-(2-propyl)oxy-5,8-dimethyl-6-(3-methylsulfonyl-1-oxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxide[Compound No. B-69]

[0444] The target compound was prepared in the same manner as describedin Example II-24 except that4-(2-propyl)oxy-5,8-dimethyl-6-(3-methylthio-1-oxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxidewas used instead of4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0445] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-70 Synthesis of4-(2-propyl)oxy-5,8-dimethyl-6-(3-benzylthio-1-oxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxide[Compound No. B-70]

[0446] The target compound was prepared in the same manner as describedin Example II-2 except that4-(2-propyl)oxy-5,8-dimethyl-6-(3-chloro-1-oxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxideand benzylthiol were used instead of4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxideand ethanethiol, respectively.

[0447] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-71 Synthesis of4-(2-propyl)oxy-5,8-dimethyl-6-(3-benzylsulfonyl-1-oxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxide[Compound No. B-71]

[0448] The target compound was prepared in the same manner as describedin Example II-24 except that4-(2-propyl)oxy-5,8-dimethyl-6-(3-benzylthio-1-oxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxidewas used instead of4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0449] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-72 Synthesis of4-methoxyimino-5-methyl-6-(3-chloro-1-oxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxide[Compound No. B-72]

[0450] The target compound was prepared in the same manner as describedin Example II-1 except that4-methoxyimino-5-methyl-6-(1,3-dioxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxidewas used instead of4-chloro-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0451] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-73 Synthesis of4-methoxyimino-5-methyl-6-(3-methylthio-1-oxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxide[Compound No. B-73]

[0452] The target compound was prepared in the same manner as describedin Example II-2 except that4-methoxyimino-5-methyl-6-(3-chloro-1-oxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxideand methanethiol were used instead of4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxideand ethanethiol, respectively.

[0453] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-74 Synthesis of4-methoxyimino-5-methyl-6-(3-phenylthio-1-oxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxide[Compound No. B-74]

[0454] The target compound was prepared in the same manner as describedin Example II-2 except that4-methoxyimino-5-methyl-6-(3-chloro-1-oxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxideand benzenethiol were used instead of4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxideand ethanethiol, respectively.

[0455] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-75 Synthesis of4-methoxyimino-5-methyl-6-(3-phenylsulfonyl-1-oxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxide[Compound No. B-75]

[0456] The target compound was prepared in the same manner as describedin Example II-24 except that4-methoxyimino-5-methyl-6-(3-phenylthio-1-oxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxidewas used instead of4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0457] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-76 Synthesis of4-methoxyimino-5-methyl-6-[3-(N-methoxymethyl)amino-1-oxocyclohexan-2-yl]carbonylthiochroman-1,1-dioxide[Compound No. B-76]

[0458] The target compound was prepared in the same manner as describedin Example II-12 except that4-methoxyimino-5-methyl-6-(3-chloro-1-oxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxidewas used instead of4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0459] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-77 Synthesis of5-chloro-6-(3-chloro-1-oxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxide[Compound No. B-77]

[0460] The target compound was prepared in the same manner as describedin Example II-1 except that5-chloro-6-(1,3-dioxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxide wasused instead of4-chloro-5-(1,3-dioxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0461] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-78 Synthesis of5-chloro-6-(3-phenylthio-1-oxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxide[Compound No. B-78]

[0462] The target compound was prepared in the same manner as describedin Example II-2 except that5-chloro-6-(3-chloro-1-oxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxideand benzenethiol were used instead of4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxideand ethanethiol.

[0463] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-79 Synthesis of5-chloro-6-(3-methylthio-1-oxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxide[Compound No. B-79]

[0464] The target compound was prepared in the same manner as describedin Example II-2 except that5-chloro-6-(3-chloro-1-oxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxideand methanethiol were used instead of4-chloro-5-(3-chloro-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxideand ethanethiol.

[0465] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-80 Synthesis of5-chloro-6-(3-methylsulfonyl-1-oxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxide[Compound No. B-80]

[0466] The target compound was prepared in the same manner as describedin Example II-24 except that5-chloro-6-(3-methylthio-1-oxocyclohexan-2-yl)carbonylthiochroman-1,1-dioxidewas used instead of4-chloro-5-(3-methylthio-1-oxocyclohexan-2-yl)carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide.

[0467] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

Example II-81 Synthesis of4-chloro-5-[3-(3-methylthio)propylthio-1-oxocyclohexan-2-yl]carbonyl-2,3-dihydrobenzothiophene-1,1-dioxide[Compound No. B-81]

[0468] The target compound was prepared in the same manner as describedin Example II-2 except that 3-methylthiopropanethiol was used instead ofethanethiol.

[0469] The obtained target compound was subjected to ¹H-NMR (CDCl₃; TMSstandard) and infrared spectrometry. The results of analysis, and thechemical structure and measured melting point of the compound are shownin Table II-1.

[0470] In the Table II-1, “(1)” to “(6)” indicates respectively asfollows.

[0471] (1) Example No.

[0472] (2) Compound No.

[0473] (3) Chemical structure

[0474] (4) NMR/ppm (CDCl₃, TMS standard)

[0475] (5) Infra Red Absorption (cm⁻¹)

[0476] (6) Property (mp: ° C.) TABLE II-1 (1) (2) (3) (4) (5) (6) II-1B-1

2.0-2.4 (2H, m) 2.4-2.7 (2H, m) 2.8-3.0 (2H, m) 3.3-3.7 (4H, m) 7.70(1H, d) 7.82 (1H, d) 1685 1605 1390 1300 1175 1125  83.8-85.4 II-2 B-2

1.37 (3H, t) 2.0-2.3 (2H, m) 2.3-2.6 (2H, m) 2.8-3.1 (4H, m) 3.2-3.7(4H, m) 7.49 (1H, d) 7.67 (1H, d) 1645 1395 1345 1305 1190 1120129.5-131.3 II-3 B-3

1.8-2.2 (2H, m) 2.3-2.6 (4H, m) 3.2-3.7 (4H, m) 7.3-7.8 (7H, m) 16501490 1415 1400 1310 1185 203.8-205.0 II-4 B-4

2.0-2.4 (2H, m) 2.4-2.7 (2H, m) 2.62 (3H, s) 2.8-3.0 (2H, m) 3.2-3.7(4H, m) 7.54 (1H, s) 1660 1610 1300 1280 1135 1120 169.9-170.4 II-5 B-5

1.9-2.1 (2H, m) 2.3-2.6 (4H, m) 2.63 (3H, s) 3.2-3.7 (4H, m) 7.31 (1H,s) 7.4-7.7 (5H, m) 1660 1640 1345 1290 1195 1125 261.9-263.7 II-6 B-6

2.0-2.4 (2H, m) 2.4-2.7 (2H, m) 2.9-3.2 (2H, m) 3.3-3.8 (4H, m) 7.69(1H, d) 7.85 (1H, d) 1670 1615 1415 1400 1315 1290 1190 1135  68.4-69.7II-7 B-7

2.0-2.3 (2H, m) 2.3-2.6 (2H, m) 2.47 (3H, s) 2.8-3.0 (2H, m) 3.2-3.7(4H, m) 7.46 (1H, d) 7.67 (1H, d) 1655 1615 1440 1400 1345 1295 1175181.8-182.5 II-8 B-8

1.06 (3H, t) 1.5-1.9 (2H, m) 2.0-2.5 (2H, m) 2.5-2.6 (2H, m) 2.8-3.1(4H, m) 3.2-3.7 (4H, m) 7.49 (1H, d) 7.67 (1H, d) 1645 1395 1345 13001240 1180   57-69 II-9 B-9

1.39 (6H, d) 2.0-2.3 (2H, m) 2.3-2.6 (2H, m) 2.8-3.1 (2H, m) 3.2-3.8(5H, m) 7.54 (1H, d) 7.68 (1H, d) 1645 1395 1345 1300 1240 1180   61-72II-10 B-10

0.95 (3H, t) 1.2-1.9 (4H, m) 1.9-2.5 (2H, m) 2.5-2.6 (2H, m) 2.8-3.1(4H, m) 3.2-3.7 (4H, m) 7.49 (1H, d) 7.67 (1H, d) 1635 1450 1390 13001175 1120 Syrup II-11 B-11

1.9-2.3 (2H, m) 2.3-2.6 (2H, m) 2.8-3.1 (2H, m) 3.2-3.7 (4H, m) 4.18(2H, s) 7.34 (5H, s) 7.45 (1H, d) 7.65 (1H, d) 1625 1395 1335 1290 11651110 191.5-192.1 II-12 B-12

1.8-2.2 (2H, m) 2.2-2.4 (2H, m) 2.6-2.9 (2H, m) 3.31 (3H, s) 3.3-3.7(4H, m) 3.68 (3H, s) 7.60 (1H, d) 7.61 (1H, d) 1585 1385 1300 1175 1120 74.3-82.5 II-13 B-13

1.8-2.1 (2H, m) 2.1-2.4 (2H, m) 2.7-2.9 (2H, m) 3.26 (6H, s) 3.2-3.7(4H, m) 7.33 (1H, d) 7.63 (1H, d) 1585 1390 1295 1170 1115 175.1-175.3II-14 B-14

1.8-2.1 (2H, m) 2.3-2.6 (4H, m) 2.42 (3H, s) 3.2-3.7 (4H, m) 7.25 (2H,d) 7.44 (2H, d) 7.53 (1H, d) 7.70 (1H, d) 1660 1630 1470 1400 1340 13101280 1250 183.3-199.5 II-15 B-15

1.8-2.2 (2H, m) 2.3-2.6 (4H, m) 2.41 (3H, s) 3.2-3.7 (4H, m) 7.34 (4H,s) 7.54 (1H, d) 7.71 (1H, d) 1640 1340 1295 1275 1245 1175 1120190.2-196.6 II-16 B-16

1.8—2.1 (2H, m) 2.2-2.6 (4H, m) 2.44 (3H, m) 3.2-3.7 (4H, m) 7.1-7.5(4H, m) 7.56 (1H, d) 7.72 (1H, d) 1640 1405 1350 1340 1305 1280 11951125 198.8-199.5 II-17 B-17

1.8-2.2 (2H, m) 2.3‘2.6 (4H, m) 3.2-3.7 (4H, m) 7.3-7.8 (6H, m) 16401495 1400 1295 1170 1110   190-192 II-18 B-18

1.24 (6H, d) 1.8-2.1 (2H, m) 2.2-2.6 (4H, m) 3.2-3.7 (5H, m) 7.1-7.6(4H, m) 7.59 (1H, d) 7.73 (1H, d) 1645 1470 1410 1395 1305 1175 112063-decop. II-19 B-19

1.8-2.2 (2H, m) 2.3-2.7 (4H, m) 3.2-3.7 (4H, m) 3.90 (3H, s) 7.5-7.8(5H, m) 7.8-8.0 (1H, m) 1725 1665 1415 1290 1255 1180 1120 186 II-20B-20

1.8-2.1 (2H, m) 2.3-2.6 (4H, m) 3.3-3.7 (4H, m) 3.86 (3H, s) 6.96 (2H,d) 7.46 (2H, d) 7.34 (1H, d) 7.70 (1H, d) 1585 1480 1400 1340 1280 12401170 117-decomp. II-21 B-21

1.8-2.2 (2H, m) 2.3-2.6 (4H, m) 3.2-3.7 (4H, m) 7.3-7.8 (6H, m) 14901420 1355 1320 1260 1180 1135 196 II-22 B-22

1.9-2.3 (2H, m) 2.3-2.6 (2H, m) 2.8-3.1 (2H, m) 3.2-3.7 (6H, m) 5.2-5.5(2H, m) 5.6-6.2 (1H, m) 7.50 (1H, d) 7.67 (1H, d) 1630 1405 1345 12951175 1120 II-23 B-23

1.44 (9H, s) 2.0-2.3 (2H, m) 2.4-2.6 (2H, m) 2.8-3.1 (2H, m) 3.3-3.7(4H, m) 7.69 (2H, s) 2960 1660 1390 1310 1290 1175 1130   151-153 II-24B-24

2.1-2.4 (2H, m) 2.5-2.7 (2H, m) 2.8-3.0 (2H, m) 2.09 (3H, s) 3.3-3.7(4H, m) 7.72 (1H, d) 8.09 (1H, d) 1665 1580 1390 1295 1175 1120  102-103 II-25 B-25

1.15 (3H, d) 2.2-3.1 (5H, m) 3.3-3.8 (4H, m) 7.70 (1H, d) 7.79 (1H, d)1690 1660 1420 1310 1290 1130 Syrup II-26 B-26

0.96 (3H, d) 2.0-2.7 (5H, m) 3.3-3.7 (4H, m) 7.5-7.6 (5H, m) 7.54 (1H,d) 7.70 (1H, d) 1650 1530 1310 1280 1260 1240 1180 1120 Syrup II-27 B-27

1.34 (3H, t) 2.2-2.4 (2H, m) 2.5-2.7 (2H, m) 2.8-3.0 (2H, m) 3.18 (2H,q) .3-3.7 (4H, m) 7.71 (1H, d) 8.09 (1H, d) 2970 1730 1680 1450 13101280 1180 1130 Syrup II-28 B-28

1.33 (3H, t) 2.1-2.4 (4H, m) 2.5-2.7 (2H, m) 2.8-3.0 (2H, m) 3.3-3.7(6H, m) 7.72 (1H, d) 8.09 (1H, d) 2980 1720 1700 1400 1310 1290 1180Syrup II-29 B-29

1.18 (6H, m) 1.8-2.1 (2H, m) 2.4-2.8 (3H, m) 3.0-3.2 (2H, m) 3.4-3.7(4H, m) 7.74 (1H, d) 8.09 (1H, d) 2970 1700 1680 1400 1320 1310 1180Syrup II-30 B-30

1.03 (3Ht) 1.2-3.8 (16H, m) 7.74 (1H, d) 8.09 (1H, d) 2970 1730 17001400 1310 Syrup II-31 B-31

1.8-2.0 (2H, m) 2.1-2.8 (4H, m) 3.4-3.7 (4H, m) 7.5-8.2 (7H, m) 29901730 1700 1400 1310 1280 1150 Syrup II-32 B-32

2.1-2.4 (2H, m) 2.4-2.8 (4H, m) 2.48 (3H, s) 3.3-3.7 (4H, m) 7.5-7.8(5H, m) 8.1-8.2 (1H, m) 3000 1730 1700 1390 1310 1280 1150 Syrup II-33B-33

2.0-2.3 (2H, m) 2.4-2.8 (4H, m) 2.48 (3H, s) 3.3-3.7 (4H, m) 7.5-7.8(5H, m) 8.1-8.2 (1H, m) 3000 1730 1700 1390 1310 1280 1150 Syrup II-34B-34

2.0-2.3 (2H, m) 2.4-2.8 (4H, m) 2.47 (3H, s) 3.3-3.7 (4H, m) 7.40 (2H,d) 7.7-7.9 (3H, m) 8.16 (1H, d) 1690 1600 1400 1310 1280 1180 1150 SyrupII-35 B-35

2.1-2.3 (2H, m) 2.5-2.8 (4H, m) 3.3-3.7 (4H, m) 7.4-7.8 (4H, m) 8.0-8.1(2H, m) 2970 1730 1700 1570 1400 1310 1280 Syrup II-36 B-36

1.23 (6H, d) 2.0-2.3 (3H, m) 2.4-2.7 (4H, m) 3.3-3.7 (4H, m) 7.3-8.2(6H, m) 2990 2900 1680 1390 1310 1280 1120 Syrup II-37 B-37

2.0-2.2 (2H, m) 2.4-2.8 (4H, m) 3.4-3.7 (4H, m) 3.90 (3H, s) 7.0-7.1(2H, m) 7.7-7.9 (3H, m) 8.16 (1H, d) 1730 1700 1390 1310 1280 1180 1150Syrup II-38 B-38

2.1-2.4 (2H, m) 2.5-2.7 (2H, m) 2.8-2.9 (2H, m) 3.4-3.7 (4H, m) 3.94(2H, d) 5.4-6.2 (3H, m) 7.72 (1H, d) 8.06 (1H, d) 1690 1660 1590 15001320 1300 1150 Syrup II-39 B-39

1.42 (9H, s) 2.1-2.4 (2H, m) 2.5-2.7 (2H, m) 2.8-2.9 (2H, m) 3.4-3.7(4H, m) 7.72 (1H, d) 8.13 (1H, d) 2960 1690 1300 1280 1180 1130 1100 810 Syrup II-40 B-40

1.7-2.3 (4H, m) 2.3-2.6 (2H, m) 3.4-3.7 (4H, m) 4.48 (2H, s) 7.4-7.6(5H, m) 7.72 (1H, d) 8.05 (1H, d) 2990 2900 1680 1390 1310 1280 1120Syrup II-41 B-41

1.9-2.2 (2H, m) 2.3-2.6 (4H, m) 3.4-3.8 (4H, m) 6.95 (2H, d) 7.45 (2H,d) 7.65 (1H, d) 7.71 (1H, d) II-42 B-42

2.0-2.3 (2H, m) 2.5-2.8 (4H, m) 3.3-3.7 (4H, m) 7.74 (1H, d) 7.78 (4H,s) 8.16 (1H, d) 1690 1570 1390 1310 1280 1180 1150 Syrup II-43 B-43

2.0-2.2 (2H, m) 2.4-2.8 (4H, m) 3.3-3.7 (4H, m) 6.96 (2H, d) 7.73 (2H,d) 7.74 (1H, d) 8.15 (1H, d) 3300 1690 1600 1580 1310 1280 1150 syrupII-44 B-44

2.1-2.4 (2H, m) 2.5-2.8 (4H, m) 3.4-3.7 (4H, m) 3.92 (3H, s) 7.6-7.8(4H, m) 8.0-8.2 (2H, m) 1720 1700 1670 1310 1280 1150 1140 1100 SyrupII-45 B-45

1.9-2.2 (2H, m) 2.3-2.5 (4H, m) 2.65 (3H, s) 3.4-3.7 (4H, m) 7.57 (2H,d) 7.66 (1H, d) 7.72 (1H, d) 8.03 (2H, d) 1690 1680 1650 1540 1400 13001290 1280 Syrup II-46 B-46

2.0-2.3 (2H, m) 2.5-2.8 (4H, m) 2.68 (3H, s) 3.4-3.7 (4H, m) 7.77 (1H,d) 8.0-8.3 (5H, m) 2980 2900 1690 1400 1310 1280 1150 Syrup II-47 B-47

2.1-2.4 (2H, m) 2.4-2.7 (2H, m) 2.54 (3H, s) 2.8-3.0 (2H, m) 3.2-3.7(4H, m) 7.58 (2H, s) 1695 1675 1295 1195 1120  890   174-176 II-48 B-48

1.8-2.1 (2H, m) 2.2-2.8 (4H, m) 3.2-3.6 (4H, m) 6.23 (1H, s) 6.7-7.8(6H, m) 3400 1650 1570 1460 1450 1450 1340 1310 syrup II-49 B-49

1.9-2.2 (2H, m) 2.3-2.5 (2H, m) 2.8-3.0 (2H, m) 3.3-3.7 (4H, m) 7.2-8.6(6H, m) 2960 1680 1570 1410 1300 1260 1130   137-139 II-50 B-50

1.24 (3H, t) 2.0-2.3 (2H, m) 2.4-2.6 (2H, m) 2.6-2.8 (2H, m) 3.3-3.7(4H, m) 4.08 (2H, q) 7.65 (2H, s) 1690 1580 1380 1360 1310 1130 1040180-decomp. II-51 B-51

1.14 (6H, d) 2.0-2.3 (2H, m) 2.4-2.6 (2H, m) 2.7-2.8 (2H, m) 3.3-3.7(4H, m) 4.62 (1H, m) 7.64 (2H, s) 1680 1640 1560 1400 1380 1300 1240  170-174 II-52 B-52

2.0-2.3 (2H, m) 2.4-2.5 (2H, m) 2.7-2.9 (2H, m) 3.3-3.7 (4H, m) 3.87(3H, s) 7.66 (2H, s) 1680 1640 1580 1380 1300 1120 powder II-53 B-53

1.9-2.2 (2H, m) 2.3-2.6 (2H, m) 2.7-2.9 (2H, m) 3.29 (3H, s) 3.3-3.7(6H, m) 4.1-4.2 (2H, m) 7.66 (2H, s) 1680 1640 1570 1410 1280 1180Powder II-54 B-54

2.0-2.3 (2H, m) 2.4-2.8 (2H, m) 2.8-3.0 (2H, m) 2.72 (3H, s) 2.78 (3H,s) 3.37 (4H, s) 4.07 (3H, s) 7.24 (1H, s) II-55 B-55

1.8-2.1 (2H, m) 2.2-2.4 (2H, m) 2.44 (3H, s) 2.63 (3H, s) 2.6-2.8 (2H,m) 3.19 (6H, s) 3.29 (4H, s) 3.99 (3H, s) 6.98 (1H, s) II-56 B-56

2.0-2.3 (2H, m) 2.3-2.5 (2H, m) 2.8-3.0 (2H, m) 2.40 (3H, s) 2.46 (3H,s) 2.77 (3H, s) 3.37 (4H, s) 4.05 (3H, s) 7.02 (1H, s) II-57 B-57

1.9-2.2 (2H, m) 2.3-2.6 (2H, m) 2.6-2.8 (2H, m) 2.62 (3H, s) 2.68 (3H,s) 3.32 (4H, s) 3.36 (3H, s) 3.63 (3H, s) 4.02 (3H, s) 7.24 (1H, s)II-58 B-58

1.8-2.1 (2H, m) 2.3-2.9 (4H, m) 2.40 (3H, s) 2.69 (3H, s) 3.37 (4H, s)4.00 (3H, s) 6.90 (1H, s) 7.19 (2H, d) 7.32 (2H, d) II-59 B-59

1.8-2.1 (2H, m) 2.3-2.8 (4H, m) 2.45 (3H, s) 2.60 (1.5H, s) 2.70 (1.5H,s) 3.35 (4H, s) 4.09 (3H, s) 7.12 (1H, s) 7.28 (2H, d) 7.46 (2H, d)

II-60 B-60

2.0-2.3 (2H, m) 2.4-2.8 (4H, m) 2.49 (3H, s) 2.68 (1.5H, s) 2.72 (1.5H,s) 2.73 (3H, s) 3.3-3.4 (4H, m) 4.04 (3H, s) 7.20 (1H, s) 7.38 (2H, d)7.77 (2H, d)

II-61 B-61

1.05 (3H, t) 1.5-1.9 (2H, m) 2.0-2.7 (6H, m) 2.51 (3H, s) 2.64 (3H, s)2.8-3.0 (2H, m) 3.36 (4H, s) 4.03 (3H, s) 7.04 (1H, s) II-62 B-62

1.10 (3H, t) 1.7-2.0 (2H, m) 2.2-2.4 (2H, m) 2.6-2.8 (2H, m) 2.64 (3H,s) 2.66 (3H, s) 2.8-3.0 (2H, m) 3.0-3.4 (6H, m) 4.08 (3H, s) 7.32 (1H,s) II-63 B-63

1.48 (6H, s) 2.0-2.4 (2H, m) 2.4-2.6 (2H, m) 2.61 (3H, s) 2.8-3.0 (2H,m) 3.46 (2H, s) 7.69 (1H, d) 7.85 (1H, d) 2980 1720 1680 1620 1320 12901190 1030   178-180 II-64 B-64

1.48 (6H, s) 1.5-2.2 (4H, m) 2.3-2.6 (2H, m) 2.51 (3H, s) 3.46 (2H, s)7.46 (4H, s) 7.51 (1H, d) 7.82 (1H, d) 3000 2980 1700 1640 1590 15601310 1290   209-211 II-65 B-65

1.48 (6H, s) 1.9-2.2 (2H, m) 2.3-2.6 (2H, m) 2.35 (3H, s) 2.7-2.9 (2H,m) 3.48 (2H, s) 7.4-7.9 (6H, m) 3000 2980 1730 1690 1560 1320 1200 II-66B-66

1.2-1.4 (6H, m) 2.0-3.0 (8H, m) 2.57 (3H, s) 2.73 (3H, s) 3.0-3.4 (1H,m) 3.7-4.2 (2H, m) 4.8-5.0 (1H, m) 7.25 (1H, s) 2980 2940 1690 1660 16101300 1280 1110   198-199 II-67 B-67

1.2-1.4 (6H, m) 2.0-2.2 (2H, m) 2.4-3.0 (6H, m) 2.42 (3H, s) 2.46 (3H,s) 2.70 (3H, s) 3.0-3.3 (1H, m) 3.7-4.2 (2H, m) 4.8-4.9 (1H, m) 7.08(1H, s) 2980 2940 1640 1350 1280 1190 1120 1050  960  910 Syrup II-68B-68

1.2-1.4 (6H, m) 1.8-2.1 (2H, m) 2.3-2.8 (6H, m) 2.41 (3H, s) 2.74 (3H,s) 3.1-3.3 (1H, m) 3.7-4.1 (2H, m) 4.8-5.0 (1H, m) 7.17 (1H, s) 7.4-7.6(5H, m) 2980 2940 1730 1660 1440 1280 1260 1190 1120 1050 Syrup II-69B-69

1.2-1.4 (6H, m) 1.9-2.2 (2H, m) 2.3-2.9 (6H, m) 2.55 (3H, s) 2.73 (3H,s) 3.01 (3H, s) 3.1-3.4 (1H, m) 3.7-4.2 (2H, m) 4.9-5.0 (1H, m) 7.49(1H, s) 2980 2940 1720 1700 1440 1380 1320 1300 1140 1120 Syrup II-70B-70

1.2-1.4 (6H, m) 2.0-2.2 (2H, m) 2.4-3.0 (6H, m) 2.47 (3H, s) 2.60 (3H,s) 3.0-3.3 (1H, m) 3.7-4.0 (2H, m) 4.12 (2H, s) 4.8-4.9 (1H, m) 7.01(1H, s) 7.2-7.3 (5H, m) 2980 2940 1660 1450 1340 1300 1280 1190 11201050  910 syrup II-71 B-71

1.2-1.4 (6H, m) 1.8-2.0 (2H, m) 2.0-2.8 (6H, m) 2.65 (3H, s) 2.70 (3H,s) 3.1-3.4 (1H, m) 3.7-4.2 (2H, m) 4.48 (2H, s) 4.9-5.0 (1H, m) 7.32(1H, s) 7.3-7.6 (5H, m) 2980 2930 1660 1450 1290 1270 1160 1120 1050 910  750 Syrup II-72 B-72

2.1-2.4 (2H, m) 2.4-2.6 (2H, m) 2.72 (3H, s) 2.8-3.0 (2H, m) 3.33 (4H,s) 4.07 (3H, s) 7.55 (1H, d) 7.87 (1H, d) 2940 1700 1670 1620 1420 13101280 1180 Syrup II-73 B-73

2.0-2.3 (2H, m) 2.4-2.6 (2H, m) 2.45 (3H, s) 2.58 (3H, s) 2.8-3.0 (2H,m) 3.32 (4H, m) 4.05 (3H, s) 7.30 (1H, d) 7.83 (1H, d) 2940 1660 15301350 1280 1220 1180 1150 1040 Syrup II-74 B-74

1.8-2.1 (2H, m) 2.3-2.5 (4H, m) 2.64 (3H, s) 3.33 (4H, s) 4.06 (3H, s)7.39 (1H, d) 7.4-7.6 (5H, m) 7.85 (1H, d) 2940 1740 1660 1520 1410 13401310 1240 Syrup II-75 B-75

2.0-2.2 (2H, m) 2.4-2.9 (4H, m) 2.43 (1.5H, s) 2.87 (1.5H, s) 3.33 (4H,s) 4.04 (1.5H, s) 4.08 (1.5H, s) 7.2-8.0 (7H, m)

2940 1680 1560 1450 1420 1310 1280 1150 1120 Syrup II-76 B-76

1.9-2.2 (2H, m) 2.2-2.5 (2H, m) 2.6-2.8 (2H, m) 2.70 (3H, s) 3.26 (3H,s) 3.31 (4H, s) 3.56 (3H, s) 4.05 (3H, s) 7.59 (1H, d) 7.78 (1H, d) 29801670 1590 1410 1310 1280 1190 1120  970  890 powder II-77 B-77

2.0-2.3 (2H, m) 2.4-2.8 (4H, m) 2.8-3.2 (4H, m) 3.3-3.5 (2H, m) 7.67(1H, d) 7.94 (1H, d) 1690 1670 1610 1310 1290 1140   185-190 II-78 B-78

1.9-2.1 (2H, m) 2.3-2.7 (6H, m) 2.9-3.2 (2H, m) 3.2-3.5 (2H, m) 7.48(1H, d) 7.5-7.6 (5H, m) 7.94 (1H, d) 1680 1660 1470 1340 1310 1290 1280II-79 B-79

2.0-2.3 (2H, m) 2.4-2.7 (4H, m) 2.50 (3H, s) 2.9-3.2 (4H, m) 3.3-3.5(2H, m) 7.35 (1H, d) 7.90 (1H, d) powder II-80 B-80

2.1-2.3 (2H, m) 2.4-2.7 (4H, m) 2.8-3.2 (4H, m) 3.09 (3H, s) 3.3-3.5(2H, m) 7.98 (2H, s) 1680 1380 1310 1140  930  820 syrup II-81 B-81

1.9-2.3 (4H, m) 2.11 (3H, s) 2.4-2.8 (4H, m) 2.9-3.2 (4H, m) 3.2-3.7(4H, m) 7.50 (1H, d) 7.69 (1H, d) 1655 1345 1305 1280 1180 1135

Example II-82˜161

[0477] Biological tests of Herbicide were carried out in the same manneras described in Example I-22, except that the respective triketonederivatives prepared in Examples II-1 to II-81 were used instead of theherbicide prepared in Example I-22.

[0478] The results of the biological tests are shown in Table II-2.

[0479] In the Table II-2, “(1)” to “(11)” indicates respectively asfollows.

[0480] (1) Example No.

[0481] (2) Compound No.

[0482] (3) Dose (g/ha)

[0483] (4) Treatment performed 3 days after transplantation

[0484] (5) Treatment performed 10 days after transplantation

[0485] (6) Weed-killing effect

[0486] (7) Chemical injury

[0487] (8) Echinochloa crug-galli

[0488] (9) Scirups juncoides

[0489] (10) Transplanted paddy rice plant TABLE II-2 (4) (5) (6) (7) (6)(1) (2) (3) (8) (9) (10) (8) (9) II- B-1 100 5 5 0 4 5  82 200 5 5 0 5 5II- B-2 100 4 5 0 3 4  83 200 5 5 0 4 5 II- B-3 100 3 4 0 3 4  84 200 45 0 4 5 II- B-4 100 5 5 1 4 5  85 200 5 5 2 5 5 II- B-5 100 4 4 0 3 4 86 200 4 4 0 4 4 II- B-6 100 5 5 0 4 5  87 200 5 5 0 5 5 II- B-7 100 45 0 4 4  88 200 5 5 0 4 5 II- B-8 100 4 5 0 4 5  89 200 5 5 0 4 5 II-B-9 100 4 5 0 4 4  90 200 5 5 0 4 5 II- B-10 100 3 4 0 3 4  91 200 5 5 04 5 II- B-11 100 3 4 0 3 4  92 200 4 5 0 3 5 II- B-12 100 5 5 0 5 5  93200 5 5 1 5 5 II- B-13 100 3 4 0 3 4  94 200 4 4 0 3 4 II- B-14 100 3 40 3 4  95 200 4 5 0 4 5 II- B-15 100 3 4 0 3 4  96 200 4 5 0 4 5 II-B-16 100 3 4 0 3 4  97 200 4 5 0 4 5 II- B-17 100 3 4 0 3 4  98 200 4 50 4 5 II- B-18 100 3 4 0 3 4  99 200 4 4 0 4 4 II- B-19 100 3 4 0 3 4100 200 4 4 0 4 4 II- B-20 100 3 4 0 3 4 101 200 4 5 0 4 5 II- B-21 1003 4 0 3 4 102 200 4 5 0 4 5 II- B-22 100 4 5 0 4 5 103 200 5 5 0 5 5 II-B-23 100 4 5 0 4 5 104 200 5 5 0 5 5 II- B-24 100 5 5 0 4 5 105 200 5 50 5 5 II- B-25 100 5 5 0 4 5 106 200 5 5 1 5 5 II- B-26 100 4 4 0 4 4107 200 5 5 0 4 5 II- B-27 100 5 5 0 4 5 108 200 5 5 0 5 5 II- B-28 1004 4 0 4 4 109 200 5 5 0 4 5 II- B-29 100 4 4 0 4 4 110 200 5 5 0 4 5 II-B-30 100 4 4 0 3 4 111 200 4 5 0 4 5 II- B-31 100 4 4 0 3 4 112 200 4 50 4 5 II- B-32 100 3 4 0 3 4 113 200 4 5 0 4 5 II- B-33 100 4 4 0 3 4114 200 4 5 0 4 5 II- B-34 100 4 4 0 3 4 115 200 4 5 0 4 5 II- B-35 1003 4 0 3 4 116 200 4 5 0 4 5 II- B-36 100 3 4 0 3 4 117 200 4 5 0 4 4 II-B-37 100 4 4 0 3 4 118 200 4 5 0 4 5 II- B-38 100 5 5 0 4 5 119 200 5 50 5 5 II- B-39 100 5 5 0 4 5 120 200 5 5 0 5 5 II- B-40 100 4 4 0 3 4121 200 5 5 0 5 5 II- B-41 100 3 4 0 3 4 122 200 4 5 0 4 5 II- B-42 1004 4 0 3 4 123 200 4 5 0 4 5 II- B-43 100 4 4 0 3 4 124 200 4 5 0 4 5 II-B-44 100 3 4 0 3 4 125 200 4 5 0 4 4 II- B-45 100 3 4 0 3 4 126 200 4 50 4 5 II- B-46 100 4 4 0 3 4 127 200 4 5 0 4 5 II- B-47 100 4 5 0 3 5128 200 5 5 0 4 5 II- B-48 100 4 4 0 3 4 129 200 4 5 0 4 5 II- B-49 1004 4 0 3 4 130 200 4 5 0 4 5 II- B-50 100 5 5 0 4 5 131 200 5 5 0 5 5 II-B-51 100 5 5 0 4 5 132 200 5 5 0 5 5 II- B-52 100 5 5 0 4 5 133 200 5 50 5 5 II- B-53 100 5 5 0 4 5 134 200 5 5 0 5 5 II- B-54 100 5 3 1 4 2135 200 5 5 4 5 5 II- B-55 100 0 0 0 0 0 136 200 1 2 0 1 2 II- B-56 1005 3 0 4 2 137 200 5 4 0 5 3 II- B-57 100 5 3 0 4 2 138 200 5 4 3 5 3 II-B-58 100 0 0 0 0 0 139 200 1 1 0 1 1 II- B-59 100 5 5 0 4 3 140 200 5 50 5 5 II- B-60 100 3 2 0 3 2 141 200 4 4 0 4 4 II- B-61 100 1 1 0 1 1142 200 5 4 0 5 3 II- B-62 100 2 1 0 2 1 143 200 5 5 0 5 4 II- B-63 1002 5 3 2 4 144 200 5 5 5 5 5 II- B-64 100 5 3 2 3 3 145 200 5 5 5 5 5 II-B-65 100 5 5 3 3 4 146 200 5 5 4 5 5 II- B-66 100 5 5 0 5 3 147 200 5 54 5 5 II- B-67 100 4 3 0 4 2 148 200 5 5 1 5 5 II- B-68 100 3 3 0 3 2149 200 5 4 0 5 4 II- B-69 100 4 4 0 4 3 150 200 5 5 1 5 5 II- B-70 1003 3 0 2 2 151 200 5 4 0 5 4 II- B-71 100 4 4 0 4 3 152 200 5 5 1 5 5 II-B-72 100 4 1 0 3 1 153 200 5 5 0 5 4 II- B-73 100 5 1 0 4 1 154 200 5 50 5 4 II- B-74 100 5 2 0 4 1 155 200 5 4 0 5 4 II- B-75 100 5 4 0 4 3156 200 5 5 1 5 5 II- B-76 100 5 3 0 4 3 157 200 5 5 1 5 5 II- B-77 1004 5 0 4 5 158 200 5 5 0 5 5 II- B-78 100 3 5 0 3 5 159 200 5 5 0 5 5 II-B-79 100 3 5 0 3 5 160 200 5 5 0 5 5 II- B-80 100 4 5 0 4 5 161 200 5 50 5 5 II- B-81 100 5 5 0 4 5 162 200 5 5 0 5 5

[0490] Industrial Applicability

[0491] As described hereinabove, the present invention provides aherbicide containing a triketone derivative as an active ingredient,which herbicide can control a wide range of weeds at a low dose andimparts a low level of chemical injury to cultivated crops, particularlya paddy rice plant.

1. A triketone derivative represented by formula [I-1]:

wherein R represents a methyl group; each of X and Y represents ahydrogen atom, a halogen atom, a nitro group, an amino group, a cyanogroup, a hydroxy group, a mercapto group, —R¹, —OR¹, —SR¹, —SO₂R¹,—NR²R³, or —NHCOR¹, wherein R¹ represents a C1-C6 alkyl group which mayhave a branched structure, a cyclic structure, or an unsaturated bond, aC1-C6 haloalkyl group which may have a branched structure, a cyclicstructure, or an unsaturated bond, a phenyl group which may besubstituted, or a benzyl group which may be substituted; each of R² andR³ represents a hydrogen atom, a C1-C6 alkyl group which may have abranched structure, a cyclic structure, or an unsaturated bond, a C1-C6haloalkyl group which may have a branched structure, a cyclic structure,or an unsaturated bond, a phenyl group which may be substituted, or abenzyl group which may be substituted, or R² and R³ may be bonded toeach other to form a group having a cyclic structure; M represents ahydrogen atom, an alkali metal, an alkaline earth metal, or an organicbase; R⁴ represents a hydrogen atom or a C1-C6 alkyl group; and m is aninteger between 0 and 4 inclusive; provided that not all of X, Y, and R⁴simultaneously represent methyl groups.
 2. A triketone derivativerepresented by formula [I-2]:

wherein R, X, Y, M, and m have the same definitions as described inrelation to formula [I-1].
 3. A triketone derivative represented byformula [I-3]:

wherein R, X, M, R⁴, and m have the same definitions as described inrelation to formula [I-1].
 4. A triketone derivative represented byformula [I-4]:

wherein R represents a methyl group; each of X and Y represents ahydrogen atom, a halogen atom, a nitro group, a cyano group, —R¹, —OR¹,—SR¹, or —NR²R³, wherein R¹ represents a C1-C6 alkyl group which mayhave a branched structure, a cyclic structure, or an unsaturated bond, aC1-C6 haloalkyl group which may have a branched structure, a cyclicstructure, or an unsaturated bond, a phenyl group which may besubstituted, or a benzyl group which may be substituted; each of R² andR³ represents a hydrogen atom, a C1-C6 alkyl group which may have abranched structure, a cyclic structure, or an unsaturated bond, a C1-C6haloalkyl group which may have a branched structure, a cyclic structure,or an unsaturated bond, a phenyl group which may be substituted, or abenzyl group which may be substituted, or R² and R³ may be bonded toeach other to form a group having a cyclic structure; Z represents —OR¹,—SO_(p)R¹, —A(CH₂)_(n)QR¹, —NR²R³, —N(OR¹)R², —O(C═O)R¹, —O(C═O)OR¹,—O(C═O)SR¹, —O(C═O)NR²R³, or —O(C═S)NR²R³ (wherein R¹, R², and R³ havethe same definitions as described in relation to X and Y, each of A andQ represents an oxygen atom or a sulfur atom, p is 0, 1, or 2, n is 1 or2), —OM (wherein M represents a hydrogen atom, an alkali metal, analkaline earth metal, or an organic base), or a halogen atom; and m isan integer between 0 and 4 inclusive.
 5. A triketone derivativeaccording to claim 4, wherein Z represents an —OM group (wherein Mrepresents a hydrogen atom, an alkali metal, an alkaline earth metal, oran organic base).
 6. A triketone derivative according to any one ofclaims 1, 2, 4, and 5, wherein Y represents a hydrogen atom, a C1-C6alkyl group, or a halogen atom.
 7. A triketone derivative according toany one of claims 1, 2, 4, and 5, wherein Y represents a hydrogen atomor a methyl group.
 8. A triketone derivative according to any one ofclaims 2, 4, and 5, wherein Y represents a hydrogen atom.
 9. A triketonederivative according to any one of claims 1 through 8, wherein Xrepresents —R¹, —OR¹, or —SR¹.
 10. A triketone derivative according toclaim 1 or 9, wherein X represents a halogen atom or a methyl group. 11.A triketone derivative according to any one of claims 1 through 10,wherein M represents a hydrogen atom.
 12. A herbicide containing atriketone derivative as recited in any one of claims 1 through 11 as anactive ingredient.
 13. A herbicide for use in cultivation of a paddyrice plant, which herbicide contains a triketone derivative as recitedin any one of claims 1 through 11 as an active ingredient.
 14. Atriketone derivative represented by formula [II-1]:

wherein R represents a methyl group; X represents a hydrogen atom, ahalogen atom, a nitro group, an amino group, a cyano group, a hydroxygroup, a mercapto group, —R¹, —OR¹, —SR¹, —SO₂R¹, —NR²R³, or —NHCOR¹(wherein R¹ represents a C1-C6 alkyl group which may have a branchedstructure, a cyclic structure, or an unsaturated bond, a C1-C6 haloalkylgroup which may have a branched structure, a cyclic structure, or anunsaturated bond, a phenyl group which may be substituted, or a benzylgroup which may be substituted; each of R² and R³ represents a hydrogenatom, a C1-C6 alkyl group which may have a branched structure, a cyclicstructure, or an unsaturated bond, a C1-C6 haloalkyl group which mayhave a branched structure, a cyclic structure, or an unsaturated bond, aphenyl group which may be substituted, or a benzyl group which may besubstituted, or R² and R³ may be bonded to each other to form a grouphaving a cyclic structure); G contains 3 to 5 ring-constituting atomswhich form a 5- to 7-membered saturated or unsaturated condensed ringincluding two carbon atoms of the benzene ring adjacent to G, whereintwo or less ring-constituting atoms are selected from among nitrogen,oxygen, and sulfur, and the ring-constituting atoms may have one or moresubstituents selected from among a C1-C6 alkyl group, a C1-C6 haloalkylgroup, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a hydroxy group,a mercapto group, an oxo group, a thioxo group, a hydroxyimino group, aC1-C6 alkoxyimino group, a hydrazono group, a C1-C6 monoalkylhydrazonogroup, and a C1-C6 dialkylhydrazono group, and a carbon atom or theadjacent carbon atom of the ring-constituting atom may have asubstituent selected from among an ethylenedioxy group, anethylenedithio group, a propylenedioxy group, and a propylenedithiogroup, with these substituents optionally being substituted with ahalogen atom or a C1-C6 alkyl group; Z¹ represents a halogen atom, —OR¹,—SO_(p)R¹, —A(CH₂)_(n)QR¹, —NR²R³, —N (OR¹) R², —O(C═O)R¹, —O(C═O)OR¹,—O(C═O)SR¹, —O(C═O)NR²R³, or —O(C═S)NR²R³ (wherein R¹, R², and R³ havethe same definitions as described in relation to X, each of A and Qrepresents an oxygen atom or a sulfur atom, p is 0, 1, or 2, n is 1 to3), or a halogen atom; m is an integer between 0 and 4 inclusive; and qis 1 or
 2. 15. A triketone derivative according to claim 14, which isrepresented by formula [II-2] or [II-3]:

wherein R, X, G, Z¹, m, and q have the same definitions as described inrelation to formula [II-1].
 16. A triketone derivative according toclaim 14 or 15, which is represented by any one of formulas [II-4] to[II-9]:

wherein R, X, G, Z¹, m, and q have the same definitions as described inrelation to formula [II-1], each of G¹ to G⁴ represents an optionallysubstituted atom that constitutes G in formula [II-1], and i is 0, 1, or2.
 17. A triketone derivative according to any one of claims 14 through16, wherein X represents a halogen atom, —R₁, —OR¹, or —SR¹.
 18. Atriketone derivative according to claim 16 or 17, wherein each of G¹ toG⁴ represents a ring-constituting atom having one or more substituentsselected from the substituent group consisting of an unsubstituted orC1-C6 alkyl group, a C1-C6 alkoxy group, an oxo group, and a C1-C6alkoxyimino group.
 19. A triketone derivative according to any one ofclaims 14 to 18, wherein Z¹ is selected from among a halogen atom, —OR¹,—SO_(p)R¹, —A(CH₂)_(n)QR¹, and —N(OR¹)R².
 20. A triketone derivativerepresented by formula [II-10]:

wherein R represents a methyl group; each of X and Y represents ahydrogen atom, a halogen atom, a nitro group, a cyano group, —R¹, —OR¹,—SR¹, or —NR²R³ (wherein R¹ represents a C1-C6 alkyl group which mayhave a branched structure, a cyclic structure, or an unsaturated bond, aC1-C6 haloalkyl group which may have a branched structure, a cyclicstructure, or an unsaturated bond, a phenyl group which may besubstituted, or a benzyl group which may be substituted, each of R² andR³ represents a hydrogen atom, a C1-C6 alkyl group which may have abranched structure, a cyclic structure, or an unsaturated bond, a C1-C6haloalkyl group which may have a branched structure, a cyclic structure,or an unsaturated bond, a phenyl group which may be substituted, or abenzyl group which may be substituted, or R² and R³ may be bonded toeach other to form a group having a cyclic structure); Z represents—OR¹, —SO_(p)R¹, —A(CH₂)_(n)QR¹, —NR²R³, —N(OR¹)R², O(C═O)R¹,—O(C═O)OR¹, —O(C═O)SR¹, —O(C═O)NR²R³, or —O(C═S)NR²R³ (wherein R¹, R²,and R³ have the same definitions as described in relation to X and Y,each of A and Q represents an oxygen atom or a sulfur atom, p is 0, 1,or 2, n is 1 or 2), —OM (wherein M represents a hydrogen atom, an alkalimetal, an alkaline earth metal, or an organic base), or a halogen atom;and m is an integer between 0 and 4 inclusive.
 21. A triketonederivative according to claim 20, wherein Y represents a hydrogen atomor a methyl group.
 22. A triketone derivative according to claim 20,wherein Y represents a hydrogen atom.
 23. A triketone derivativeaccording to any one of claims 20 through 22, wherein Z represents ahalogen atom, —OR¹, —SO_(p)R¹, —A(CH₂)_(n)QR¹, or —N(OR¹)R².
 24. Atriketone derivative according to any one of claims 14 through 23,wherein X represents a halogen atom or a methyl group.
 25. A herbicidecontaining a triketone derivative as recited in any one of claims 14through 24 as an active ingredient.
 26. A herbicide for use incultivation of a paddy rice plant, which herbicide contains a triketonederivative as recited in any one of claims 14 through 24 as an activeingredient.